# Patent

## Title
Macrocyclic picolinamides as fungicides

## Abstract

The disclosure relates to macrocyclic picolinamides of Formula (I) and to the use of these compounds as fungicides.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Patent Application Ser. No. 61/747,723 filed Dec. 31, 2012, which is expressly incorporated by reference herein.


BACKGROUND AND SUMMARY
Fungicides are compounds, of natural or synthetic origin, which act to protect and/or cure plants against damage caused by agriculturally relevant fungi. Generally, no single fungicide is useful in all situations. Consequently, research is ongoing to produce fungicides that may have better performance, are easier to use, and cost less.
The present disclosure relates to macrocyclic picolinamides and their use as fungicides. The compounds of the present disclosure may offer protection against ascomycetes, basidiomycetes, deuteromycetes and oomycetes.
One embodiment of the present disclosure may include compounds of Formula I:




X is H or C(O)R5;
Y is H, C(O)R5, or Q;
Q is




R1 is H, alkyl, alkenyl, aryl, —C(O)R4, each substituted with 0, 1 or multiple R4;
R2 is H, alkyl, alkenyl, aryl, —C(O)R4, each substituted with 0, 1 or multiple R4;
R3 is H, —C(O)R6 or —CH2OC(O)R6;
R4 is alkyl, alkenyl, halo, haloalkyl, alkoxy, or aryl;
R5 is alkyl, alkoxy, benzyl, benzyloxy, each substituted with 0, 1, or multiple R7, wherein each R7 may be substituted with 0, 1, or multiple R4;
R6 is alkyl or alkoxy, each substituted with 0, 1, or multiple R4;
R7 is alkyl, alkenyl, halo, haloalkyl, alkoxy, aryl, heteroaryl, carbocyclic, heterocyclic, —Si(R4)3, —C(O)R4, —S(O)nR4, each substituted with 0, 1, or multiple R4;
and with the proviso that when R1 and R2 are H then X and Y are C(O)R5 and R5 is tert-butoxy.
Another embodiment of the present disclosure may include a fungicidal composition for the control or prevention of fungal attack comprising the compounds described above and a phytologically acceptable carrier material.
Yet another embodiment of the present disclosure may include a method for the control or prevention of fungal attack on a plant, the method including the steps of applying a fungicidally effective amount of one or more of the compounds described above to at least one of the fungus, the plant, an area adjacent to the plant, and the seed adapted to produce the plant.
The term “alkyl” refers to a branched or unbranched carbon chain, including methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tertiary butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
The term “alkenyl” refers to a branched or unbranched carbon chain containing one or more double bonds including ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, cyclopentenyl, cyclohexenyl, and the like.
The term “alkynyl” refers to a branched or unbranched carbon chain containing one or more triple bonds including propynyl, butyryl and the like.
The term “aryl” refers to any aromatic, mono- or bi-cyclic, containing 0 heteroatoms.
The term “heterocyclyl” refers to any aromatic or non-aromatic ring, mono- or bi-cyclic, containing one or more heteroatoms
The term “cycloalkyl” refers to any monocyclic or polycyclic, saturated substituent consisting of carbon and hydrogen, for example, cyclopropyl, cyclobutyl, cyclopentyl, norbornyl, bicyclo[2.2.2]octyl, and decahydronaphthyl.
The term “cycloalkenyl” refers to any monocyclic or polycyclic, unsaturated (at least one carbon-carbon double bond) substituent consisting of carbon and hydrogen, for example, cyclobutenyl, cyclopentenyl, cyclohexenyl, norbornenyl, bicyclo[2.2.2]octenyl, tetrahydronaphthyl, hexahydronaphthyl, and octahydronaphthyl.
The term “alkoxy” refers to an —OR substituent.
The term “alkoxycarbonyl” refers to a —C(O)—OR substituent.
The term “alkylcarbonyl” refers to a —C(O)—R substituent.
The term “alkylsulfonyl” refers to an —SO2—R substituent.
The term “haloalkylsulfonyl” refers to an —SO2—R substituent where R is fully or partially substituted with Cl, F, I, or Br or any combination thereof.
The term “alkylthio” refers to an —S—R substituent.
The term “haloalkylthio” refers to an alkylthio, which is substituted with Cl, F, I, or Br or any combination thereof.
The term “alkylaminocarbonyl” refers to a —C(O)—N(H)—R substituent.
The term “dialkylaminocarbonyl” refers to a —C(O)—NR2 substituent.
The term “alkylcycloalkylamino” refers to a cycloalkylamino substituent that is substituted with an alkyl group.
The term “trialkylsilyl” refers to —SiR3.
The term “cyano” refers to a —C≡N substituent.
The term “hydroxyl” refers to an —OH substituent.
The term “amino” refers to a —NH2 substituent.
The term “alkylamino” refers to a —N(H)—R substituent.
The term “dialkylamino” refers to a —NR2 substituent.
The term “alkoxyalkoxy” refers to —O(CH2)nO(CH2)n where n is an integer selected from the list 1, 2, 3, 4, 5, or 6.
The term “alkoxyalkyl” refers to an alkoxy substitution on an alkyl.
The term “haloalkoxyalkyl” refers to an alkoxy substitution on an alkyl which may be partially substituted with halogen atoms.
The term “hydroxyalkyl” refers to an alkyl which is substituted with a hydroxyl group.
The term “haloalkoxy” refers to an —OR—X substituent, wherein X is Cl, F, Br, or I, or any combination thereof.
The term “haloalkyl” refers to an alkyl, which is substituted with Cl, F, I, or Br or any combination thereof.
The term “haloalkenyl” refers to an alkenyl, which is substituted with Cl, F, I, or Br or any combination thereof.
The term “haloalkynyl” refers to an alkynyl which is substituted with Cl, F, I, or Br or any combination thereof.
The term “halogen” or “halo” refers to one or more halogen atoms, defined as F, Cl, Br, and I.
The term “hydroxycarbonyl” refers to a —C(O)—OH substituent.
The term “nitro” refers to a —NO2 substituent.
The term “optionally substituted with” a substituent means containing 0, 1, or more of that substituent.
Unless specifically noted or clearly implied otherwise the term “about” refers to a range of values of plus or minus 10 percent, e.g. about 1 refers to the range 0.9 to 1.1.
Throughout the disclosure, reference to the compounds of Formula I is read as also including diastereomers, enantiomers, and mixtures thereof. In another embodiment, Formula (I) is read as also including salts or hydrates thereof. Exemplary salts include, but are not limited to: hydrochloride, hydrobromide, and hydroiodide.
It is also understood by those skilled in the art that additional substitution is allowable, unless otherwise noted, as long as the rules of chemical bonding and strain energy are satisfied and the product still exhibits fungicidal activity.
Another embodiment of the present disclosure is a use of a compound of Formula I, for protection of a plant against attack by a phytopathogenic organism or the treatment of a plant infested by a phytopathogenic organism, comprising the application of a compound of Formula I, or a composition comprising the compound to soil, a plant, a part of a plant, foliage, roots, and/or seeds.
Additionally, another embodiment of the present disclosure is a composition useful for protecting a plant against attack by a phytopathogenic organism and/or treatment of a plant infested by a phytopathogenic organism comprising a compound of Formula I and a phytologically acceptable carrier material.
In one embodiment, a compound of Formula (I) is provided:




wherein:
X is H or C(O)R5;
Y is H, C(O)R5, or Q;
Q is




R1 is H, alkyl, alkenyl, aryl, —C(O)R4, each optionally substituted with one or more R4;
R2 is H, alkyl, alkenyl, aryl —C(O)R4, each optionally substituted with one or more R4;
R3 is H, —C(O)R6 or —CH2OC(O)R6;
R4 is alkyl, alkenyl, halo, haloalkyl, alkoxy, or aryl;
R5 is alkyl, alkoxy, benzyl, benzyloxy, each optionally substituted with one or more R7, wherein each R7 may be optionally substituted with one or more R4;
R6 is alkyl or alkoxy, each optionally substituted with one or more R4;
R7 is alkyl, alkenyl, halo, haloalkyl, alkoxy, aryl, heteroaryl, carbocyclic, heterocyclic, and —Si(R4)3, —C(O)R4, —S(O)nR4, each optionally substituted with one or more R4;
with the proviso that when R1 and R2 are H, X and Y are C(O)R5 and R5 is tert-butoxy.
In one more particular embodiment, X and Y are independently chosen from H or C(O)R5. In an even more particular embodiment, X and Y are C(O)R5 and R5 is independently chosen from alkyl, alkoxy, benzyl, or benzyloxy, each optionally substituted with one or more R7, wherein each R7 may be optionally substituted with one or more R4. In a still more particular embodiment, R1 and R2 are independently chosen from H, alkyl, alkenyl, aryl, or —C(O)R4, each optionally substituted with one or more R4.
In one embodiment, R5 is alkoxy and R1 and R2 are H.
In one embodiment, R5 is tert-butoxy. In one embodiment, X and Y are hydrogen. In a more particular embodiment, R1 and R2 are independently chosen from H, alkyl, alkenyl, aryl, or —C(O)R4, each optionally substituted with one or more R4.
In one embodiment, R1 and R2 are independently alkyl, alkenyl, aryl, or —C(O)R4, each optionally substituted with one or more R4.
In one embodiment, R1 and R2 are independently alkyl or aryl, each optionally substituted with one or more R4.
In one embodiment, the amine is protonated to give an ammonium salt of a mineral acid independently chosen from hydrogen chloride, hydrogen bromide, or hydrogen iodide. In a more particular embodiment, the ammonium salt is the ammonium hydrochloride.
In one embodiment, X is H and Y is Q.
In one embodiment, R1 and R2 are independently chosen from H, alkyl, alkenyl, aryl, or —C(O)R4, each optionally substituted with one or more R4.
In one embodiment, R1 and R2 are independently alkyl, alkenyl, aryl, or —C(O)R4, each optionally substituted one or more R4.
In one embodiment, R1 and R2 are independently alkyl or aryl, each optionally substituted with one or more R4.
In one embodiment, R3 is H, —C(O)R6 or —CH2C(O)R6. In a more particular embodiment, R3 is H. In another more particular embodiment, R3 is C(O)R6. In a further particular embodiment, R6 is alkyl or alkoxy, each optionally substituted with one or more R4. In another further particular embodiment, R6 is alkyl, optionally substituted with one or more R4. In still another further particular embodiment, R6 is —CH3 or —CH2CH2—R4 and R4 is OCH3. In another more particular embodiment, R3 is —CH2OC(O)R6. In a further particular embodiment, R6 is alkyl or alkoxy, each optionally substituted with one or more R4. In another further particular embodiment, R6 is alkyl, each optionally substituted with one or more R4. In still another more particular embodiment, R6 is —CH3 or —CH(CH3)2.
In one embodiment, a composition is provided for the control of a fungal or fugal like pathogen. In one embodiment, the composition includes the compound of Formula I as defined by any of the above embodiments and a phytologically acceptable carrier material. The combination of Formula I and the carrier is useful for the control of fungal and fungal like pathogens. In a more particular embodiment, the fungal or fungal like pathogen is selected from the group consisting of: Mycosphaerella graminicola(Septoria tritici), Puccinia triticina, Puccinia striiformis, Venturia inaequalis, Uncinula necator, Rhynchosporium secalis, Magnaporthe grisea, Phakopsora pachyrhizi, Leptosphaeria nodorum, Blumeria graminis f. sp. tritici, Blumeria graminis f. sp. hordei, Erysiphe cichoracearum, Glomerella lagenarium, Cercospora beticola, and Alternaria solani. In a further particular embodiment, the fungal pathogen or fungal like pathogen is selected from the group consisting of: Septoria tritici and Puccinia triticina. 
In one embodiment, a method for the control and prevention of plant disease is provided. The method includes applying a fungicidally effective amount of at least one of the compounds of Formula I as defined by any of the above embodiments to at least one surface selected from the group consisting of: at least one surface of a plant, an area adjacent to a plant, soil in contact with a plant, soil adjacent to a plant, seeds, and equipment for use in agriculture. In a more particular embodiment, the fungicidally effective amount Formula I is applied to a surface in the range of about 0.01 g/m2 to about 0.45 g/m2 of Formula I.


DESCRIPTION
The compounds of the present disclosure may be applied by any of a variety of known techniques, either as the compounds or as formulations comprising the compounds. For example, the compounds may be applied to the roots, seeds or foliage of plants for the control of various fungi, without damaging the commercial value of the plants. The materials may be applied in the form of any of the generally used formulation types, for example, as solutions, dusts, wettable powders, flowable concentrate, suspension concentrates, or emulsifiable concentrates.
Preferably, the compounds of the present disclosure are applied in the form of a formulation, comprising one or more of the compounds of Formula I with a phytologically acceptable carrier. Concentrated formulations may be dispersed in water, or other liquids, for application, or formulations may be dust-like or granular, which may then be applied without further treatment. The formulations may be prepared according to procedures that are conventional in the agricultural chemical art.
The present disclosure contemplates all vehicles by which one or more of the compounds may be formulated for delivery and use as a fungicide. Typically, formulations are applied as aqueous suspensions or emulsions. Such suspensions or emulsions may be produced from water-soluble, water-suspendible, or emulsifiable formulations which are solids, usually known as wettable powders; or liquids, usually known as emulsifiable concentrates, aqueous suspensions, or suspension concentrates. As will be readily appreciated, any material to which these compounds may be added may be used, provided it yields the desired utility without significant interference with the activity of these compounds as antifungal agents.
Wettable powders, which may be compacted to form water-dispersible granules, comprise an intimate mixture of one or more of the compounds of Formula I, an inert carrier and surfactants. The concentration of the compound in the wettable powder may be from about 10 percent to about 90 percent by weight based on the total weight of the wettable powder, more preferably about 25 weight percent to about 75 weight percent. In the preparation of wettable powder formulations, the compounds may be compounded with any finely divided solid, such as prophyllite, talc, chalk, gypsum, Fuller's earth, bentonite, attapulgite, starch, casein, gluten, montmorillonite clays, diatomaceous earths, purified silicates or the like. In such operations, the finely divided carrier and surfactants are typically blended with the compound(s) and milled.
Emulsifiable concentrates of the compounds of Formula I may comprise a convenient concentration, such as from about 1 weight percent to about 50 weight percent of the compound, in a suitable liquid, based on the total weight of the concentrate. The compounds may be dissolved in an inert carrier, which is either a water-miscible solvent or a mixture of water-immiscible organic solvents, and emulsifiers. The concentrates may be diluted with water and oil to form spray mixtures in the form of oil-in-water emulsions. Useful organic solvents include aromatics, especially the high-boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, for example, terpenic solvents, including rosin derivatives, aliphatic ketones, such as cyclohexanone, and complex alcohols, such as 2-ethoxyethanol.
Emulsifiers which may be advantageously employed herein may be readily determined by those skilled in the art and include various nonionic, anionic, cationic and amphoteric emulsifiers, or a blend of two or more emulsifiers. Examples of nonionic emulsifiers useful in preparing the emulsifiable concentrates include the polyalkylene glycol ethers and condensation products of alkyl and aryl phenols, aliphatic alcohols, aliphatic amines or fatty acids with ethylene oxide, propylene oxides such as the ethoxylated alkyl phenols and carboxylic esters solubilized with the polyol or polyoxyalkylene. Cationic emulsifiers include quaternary ammonium compounds and fatty amine salts. Anionic emulsifiers include the oil-soluble salts (e.g., calcium) of alkylaryl sulphonic acids, oil-soluble salts or sulfated polyglycol ethers and appropriate salts of phosphated polyglycol ether.
Representative organic liquids which may be employed in preparing the emulsifiable concentrates of the compounds of the present disclosure are the aromatic liquids such as xylene, propyl benzene fractions; or mixed naphthalene fractions, mineral oils, substituted aromatic organic liquids such as dioctyl phthalate; kerosene; dialkyl amides of various fatty acids, particularly the dimethyl amides of fatty glycols and glycol derivatives such as the n-butyl ether, ethyl ether or methyl ether of diethylene glycol, the methyl ether of triethylene glycol, petroleum fractions or hydrocarbons such as mineral oil, aromatic solvents, paraffinic oils, and the like; vegetable oils such as soy bean oil, rape seed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cotton seed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; esters of the above vegetable oils; and the like. Mixtures of two or more organic liquids may also be employed in the preparation of the emulsifiable concentrate. Organic liquids include xylene, and propyl benzene fractions, with xylene being most preferred in some cases. Surface-active dispersing agents are typically employed in liquid formulations and in an amount of from 0.1 to 20 percent by weight based on the combined weight of the dispersing agent with one or more of the compounds. The formulations can also contain other compatible additives, for example, plant growth regulators and other biologically active compounds used in agriculture.
Aqueous suspensions comprise suspensions of one or more water-insoluble compounds of Formula I, dispersed in an aqueous vehicle at a concentration in the range from about 1 to about 50 weight percent, based on the total weight of the aqueous suspension. Suspensions are prepared by finely grinding one or more of the compounds, and vigorously mixing the ground material into a vehicle comprised of water and surfactants chosen from the same types discussed above. Other components, such as inorganic salts and synthetic or natural gums, may also be added to increase the density and viscosity of the aqueous vehicle.
The compounds of Formula I can also be applied as granular formulations, which are particularly useful for applications to the soil. Granular formulations generally contain from about 0.5 to about 10 weight percent, based on the total weight of the granular formulation of the compound(s), dispersed in an inert carrier which consists entirely or in large part of coarsely divided inert material such as attapulgite, bentonite, diatomite, clay or a similar inexpensive substance. Such formulations are usually prepared by dissolving the compounds in a suitable solvent and applying it to a granular carrier which has been preformed to the appropriate particle size, in the range of from about 0.5 to about 3 mm. A suitable solvent is a solvent in which the compound is substantially or completely soluble. Such formulations may also be prepared by making a dough or paste of the carrier and the compound and solvent, and crushing and drying to obtain the desired granular particle.
Dusts containing the compounds of Formula I may be prepared by intimately mixing one or more of the compounds in powdered form with a suitable dusty agricultural carrier, such as, for example, kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1 to about 10 weight percent of the compounds, based on the total weight of the dust.
The formulations may additionally contain adjuvant surfactants to enhance deposition, wetting and penetration of the compounds onto the target crop and organism. These adjuvant surfactants may optionally be employed as a component of the formulation or as a tank mix. The amount of adjuvant surfactant will typically vary from 0.01 to 1.0 percent by volume, based on a spray-volume of water, preferably 0.05 to 0.5 volume percent. Suitable adjuvant surfactants include, but are not limited to ethoxylated nonyl phenols, ethoxylated synthetic or natural alcohols, salts of the esters or sulphosuccinic acids, ethoxylated organosilicones, ethoxylated fatty amines, blends of surfactants with mineral or vegetable oils, crop oil concentrate (mineral oil (85%)+emulsifiers (15%)); nonylphenol ethoxylate; benzylcocoalkyldimethyl quaternary ammonium salt; blend of petroleum hydrocarbon, alkyl esters, organic acid, and anionic surfactant; C9-C11 alkylpolyglycoside; phosphated alcohol ethoxylate; natural primary alcohol (C12-C16) ethoxylate; di-sec-butylphenol EO-PO block copolymer; polysiloxane-methyl cap; nonylphenol ethoxylate+urea ammonium nitrate; emulsified methylated seed oil; tridecyl alcohol (synthetic) ethoxylate (8EO); tallow amine ethoxylate (15 EO); PEG (400) dioleate-99. The formulations may also include oil-in-water emulsions such as those disclosed in U.S. patent application Ser. No. 11/495,228, the disclosure of which is expressly incorporated by reference herein.
The formulations may optionally include combinations that contain other pesticidal compounds. Such additional pesticidal compounds may be fungicides, insecticides, herbicides, nematocides, miticides, arthropodicides, bactericides or combinations thereof that are compatible with the compounds of the present disclosure in the medium selected for application, and not antagonistic to the activity of the present compounds. Accordingly, in such embodiments, the other pesticidal compound is employed as a supplemental toxicant for the same or for a different pesticidal use. The compounds of Formula I and the pesticidal compound in the combination can generally be present in a weight ratio of from 1:100 to 100:1.
The compounds of the present disclosure may also be combined with other fungicides to form fungicidal mixtures and synergistic mixtures thereof. The fungicidal compounds of the present disclosure are often applied in conjunction with one or more other fungicides to control a wider variety of undesirable diseases. When used in conjunction with other fungicide(s), the presently claimed compounds may be formulated with the other fungicide(s), tank-mixed with the other fungicide(s) or applied sequentially with the other fungicide(s). Such other fungicides may include 2-(thiocyanatomethylthio)-benzothiazole, 2-phenylphenol, 8-hydroxyquinoline sulfate, ametoctradin, amisulbrom, antimycin, Ampelomyces quisqualis, azaconazole, azoxystrobin, Bacillus subtilis, Bacillus subtilis strain QST713, benalaxyl, benomyl, benthiavalicarb-isopropyl, benzylaminobenzene-sulfonate (BABS) salt, bicarbonates, biphenyl, bismerthiazol, bitertanol, bixafen, blasticidin-S, borax, Bordeaux mixture, boscalid, bromuconazole, bupirimate, calcium polysulfide, captafol, captan, carbendazim, carboxin, carpropamid, carvone, chlazafenone, chloroneb, chlorothalonil, chlozolinate, Coniothyrium minitans, copper hydroxide, copper octanoate, copper oxychloride, copper sulfate, copper sulfate (tribasic), cuprous oxide, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dazomet, debacarb, diammonium ethylenebis-(dithiocarbamate), dichlofluanid, dichlorophen, diclocymet, diclomezine, dichloran, diethofencarb, difenoconazole, difenzoquat ion, diflumetorim, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinobuton, dinocap, diphenylamine, dithianon, dodemorph, dodemorph acetate, dodine, dodine free base, edifenphos, enestrobin, enestroburin, epoxiconazole, ethaboxam, ethoxyquin, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumorph, fluopicolide, fluopyram, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, formaldehyde, fosetyl, fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, guazatine, guazatine acetates, GY-81, hexachlorobenzene, hexaconazole, hymexazol, imazalil, imazalil sulfate, imibenconazole, iminoctadine, iminoctadine triacetate, iminoctadine tris(albesilate), iodocarb, ipconazole, ipfenpyrazolone, iprobenfos, iprodione, iprovalicarb, isoprothiolane, isopyrazam, isotianil, kasugamycin, kasugamycin hydrochloride hydrate, kresoxim-methyl, laminarin, mancopper, mancozeb, mandipropamid, maneb, mefenoxam, mepanipyrim, mepronil, meptyl-dinocap, mercuric chloride, mercuric oxide, mercurous chloride, metalaxyl, metalaxyl-M, metam, metam-ammonium, metam-potassium, metam-sodium, metconazole, methasulfocarb, methyl iodide, methyl isothiocyanate, metiram, metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam, nitrothal-isopropyl, nuarimol, octhilinone, ofurace, oleic acid (fatty acids), orysastrobin, oxadixyl, oxine-copper, oxpoconazole fumarate, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, pentachlorophenyl laurate, penthiopyrad, phenylmercury acetate, phosphonic acid, phthalide, picoxystrobin, polyoxin B, polyoxins, polyoxorim, potassium bicarbonate, potassium hydroxyquinoline sulfate, probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb, proquinazid, prothioconazole, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriofenone, pyroquilon, quinoclamine, quinoxyfen, quintozene, Reynoutria sachalinensis extract, sedaxane, silthiofam, simeconazole, sodium 2-phenylphenoxide, sodium bicarbonate, sodium pentachlorophenoxide, spiroxamine, sulfur, SYP-Z048, tar oils, tebuconazole, tebufloquin, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin, valifenalate, valiphenal, vinclozolin, zineb, ziram, zoxamide, Candida oleophila, Fusarium oxysporum, Gliocladium spp., Phlebiopsis gigantea, Streptomyces griseoviridis, Trichoderma spp., (RS)—N-(3,5-dichlorophenyl)-2-(methoxymethyl)-succinimide, 1,2-dichloropropane, 1,3-dichloro-1,1,3,3-tetrafluoroacetone hydrate, 1-chloro-2,4-dinitronaphthalene, 1-chloro-2-nitropropane, 2-(2-heptadecyl-2-imidazolin-1-yl)ethanol, 2,3-dihydro-5-phenyl-1,4-dithi-ine 1,1,4,4-tetraoxide, 2-methoxyethylmercury acetate, 2-methoxyethylmercury chloride, 2-methoxyethylmercury silicate, 3-(4-chlorophenyl)-5-methylrhodanine, 4-(2-nitroprop-1-enyl)phenyl thiocyanateme, ampropylfos, anilazine, azithiram, barium polysulfide, Bayer 32394, benodanil, benquinox, bentaluron, benzamacril; benzamacril-isobutyl, benzamorf, binapacryl, bis(methylmercury) sulfate, bis(tributyltin) oxide, buthiobate, cadmium calcium copper zinc chromate sulfate, carbamorph, CECA, chlobenthiazone, chloraniformethan, chlorfenazole, chlorquinox, climbazole, copper bis(3-phenylsalicylate), copper zinc chromate, cufraneb, cupric hydrazinium sulfate, cuprobam, cyclafuramid, cypendazole, cyprofuram, decafentin, dichlone, dichlozoline, diclobutrazol, dimethirimol, dinocton, dinosulfon, dinoterbon, dipyrithione, ditalimfos, dodicin, drazoxolon, EBP, ESBP, etaconazole, etem, ethirim, fenaminosulf, fenapanil, fenitropan, fluotrimazole, furcarbanil, furconazole, furconazole-cis, furmecyclox, furophanate, glyodine, griseofulvin, halacrinate, Hercules 3944, hexylthiofos, ICIA0858, isopamphos, isovaledione, mebenil, mecarbinzid, metazoxolon, methfuroxam, methylmercury dicyandiamide, metsulfovax, milneb, mucochloric anhydride, myclozolin, N-3,5-dichlorophenylsuccinimide, N-3-nitrophenylitaconimide, natamycin, N-ethylmercurio-4-toluenesulfonanilide, nickel bis(dimethyldithiocarbamate), OCH, phenylmercury dimethyldithiocarbamate, phenylmercury nitrate, phosdiphen, prothiocarb; prothiocarb hydrochloride, pyracarbolid, pyridinitril, pyroxychlor, pyroxyfur, quinacetol; quinacetol sulfate, quinazamid, quinconazole, rabenzazole, salicylanilide, SSF-109, sultropen, tecoram, thiadifluor, thicyofen, thiochlorfenphim, thiophanate, thioquinox, tioxymid, triamiphos, triarimol, triazbutil, trichlamide, urbacid, zarilamid, and any combinations thereof.
Additionally, the compounds described herein may be combined with other pesticides, including insecticides, nematocides, miticides, arthropodicides, bactericides or combinations thereof that are compatible with the compounds of the present disclosure in the medium selected for application, and not antagonistic to the activity of the present compounds to form pesticidal mixtures and synergistic mixtures thereof. The fungicidal compounds of the present disclosure may be applied in conjunction with one or more other pesticides to control a wider variety of undesirable pests. When used in conjunction with other pesticides, the presently claimed compounds may be formulated with the other pesticide(s), tank-mixed with the other pesticide(s) or applied sequentially with the other pesticide(s). Typical insecticides include, but are not limited to: 1,2-dichloropropane, abamectin, acephate, acetamiprid, acethion, acetoprole, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, allyxycarb, alpha-cypermethrin, alpha-ecdysone, alpha-endosulfan, amidithion, aminocarb, amiton, amiton oxalate, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, barium hexafluorosilicate, barthrin, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin, bioethanomethrin, biopermethrin, bistrifluoron, borax, boric acid, bromfenvinfos, bromocyclen, bromo-DDT, bromophos, bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, calcium arsenate, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, carbophenothion, carbosulfan, cartap, cartap hydrochloride, chlorantraniliprole, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlordimeform hydrochloride, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloroform, chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chromafenozide, cinerin I, cinerin II, cinerins, cismethrin, cloethocarb, closantel, clothianidin, copper acetoarsenite, copper arsenate, copper naphthenate, copper oleate, coumaphos, coumithoate, crotamiton, crotoxyphos, crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate, cyantraniliprole, cyclethrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin, cyromazine, cythioate, DDT, decarbofuran, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, dialifos, diatomaceous earth, diazinon, dicapthon, dichlofenthion, dichlorvos, dicresyl, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dilor, dimefluthrin, dimefox, dimetan, dimethoate, dimethrin, dimethylvinphos, dimetilan, dinex, dinex-diclexine, dinoprop, dinosam, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, d-limonene, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, doramectin, ecdysterone, emamectin, emamectin benzoate, EMPC, empenthrin, endosulfan, endothion, endrin, EPN, epofenonane, eprinomectin, esdepalléthrine, esfenvalerate, etaphos, ethiofencarb, ethion, ethiprole, ethoate-methyl, ethoprophos, ethyl formate, ethyl-DDD, ethylene dibromide, ethylene dichloride, ethylene oxide, etofenprox, etrimfos, EXD, famphur, fenamiphos, fenazaflor, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb, fenoxacrim, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion, fenthion, fenthion-ethyl, fenvalerate, fipronil, flonicamid, flubendiamide, flucofuron, flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flufenprox, fluvalinate, fonofos, formetanate, formetanate hydrochloride, formothion, formparanate, formparanate hydrochloride, fosmethilan, fospirate, fosthietan, furathiocarb, furethrin, gamma-cyhalothrin, gamma-HCH, halfenprox, halofenozide, HCH, HEOD, heptachlor, heptenophos, heterophos, hexaflumuron, HHDN, hydramethylnon, hydrogen cyanide, hydroprene, hyquincarb, imidacloprid, imiprothrin, indoxacarb, iodomethane, IPSP, isazofos, isobenzan, isocarbophos, isodrin, isofenphos, isofenphos-methyl, isoprocarb, isoprothiolane, isothioate, isoxathion, ivermectin, jasmolin I, jasmolin II, jodfenphos, juvenile hormone I, juvenile hormone II, juvenile hormone III, kelevan, kinoprene, lambda-cyhalothrin, lead arsenate, lepimectin, leptophos, lindane, lirimfos, lufenuron, lythidathion, malathion, malonoben, mazidox, mecarbam, mecarphon, menazon, mephosfolan, mercurous chloride, mesulfenfos, metaflumizone, methacrifos, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, methoxychlor, methoxyfenozide, methyl bromide, methyl isothiocyanate, methylchloroform, methylene chloride, metofluthrin, metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin, milbemycin oxime, mipafox, mirex, molosultap, monocrotophos, monomehypo, monosultap, morphothion, moxidectin, naftalofos, naled, naphthalene, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, noviflumuron, omethoate, oxamyl, oxydemeton-methyl, oxydeprofos, oxydisulfoton, para-dichlorobenzene, parathion, parathion-methyl, penfluoron, pentachlorophenol, permethrin, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon, phosphine, phoxim, phoxim-methyl, pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, potassium arsenite, potassium thiocyanate, pp′-DDT, prallethrin, precocene I, precocene II, precocene III, primidophos, profenofos, profluralin, promacyl, promecarb, propaphos, propetamphos, propoxur, prothidathion, prothiofos, prothoate, protrifenbute, pyraclofos, pyrafluprole, pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins, pyridaben, pyridalyl, pyridaphenthion, pyrifluquinazon, pyrimidifen, pyrimitate, pyriprole, pyriproxyfen, quassia, quinalphos, quinalphos-methyl, quinothion, rafoxanide, resmethrin, rotenone, ryania, sabadilla, schradan, selamectin, silafluofen, silica gel, sodium arsenite, sodium fluoride, sodium hexafluorosilicate, sodium thiocyanate, sophamide, spinetoram, spinosad, spiromesifen, spirotetramat, sulcofuron, sulcofuron-sodium, sulfluramid, sulfotep, sulfoxaflor, sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron, tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachloroethane, tetrachlorvinphos, tetramethrin, tetramethylfluthrin, theta-cypermethrin, thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiocyclam oxalate, thiodicarb, thiofanox, thiometon, thiosultap, thiosultap-disodium, thiosultap-monosodium, thuringiensin, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triarathene, triazamate, triazophos, trichlorfon, trichlormetaphos-3, trichloronat, trifenofos, triflumuron, trimethacarb, triprene, vamidothion, vaniliprole, XMC, xylylcarb, zeta-cypermethrin, zolaprofos, and any combinations thereof.
Additionally, the compounds described herein be combined with herbicides that are compatible with the compounds of the present disclosure in the medium selected for application, and not antagonistic to the activity of the present compounds to form pesticidal mixtures and synergistic mixtures thereof. The fungicidal compounds of the present disclosure may be applied in conjunction with one or more herbicides to control a wide variety of undesirable plants. When used in conjunction with herbicides, the presently claimed compounds may be formulated with the herbicide(s), tank-mixed with the herbicide(s) or applied sequentially with the herbicide(s). Typical herbicides include, but are not limited to: 4-CPA; 4-CPB; 4-CPP; 2,4-D; 3,4-DA; 2,4-DB; 3,4-DB; 2,4-DEB; 2,4-DEP; 3,4-DP; 2,3,6-TBA; 2,4,5-T; 2,4,5-TB; acetochlor, acifluorfen, aclonifen, acrolein, alachlor, allidochlor, alloxydim, allyl alcohol, alorac, ametridione, ametryn, amibuzin, amicarbazone, amidosulfuron, aminocyclopyrachlor, aminopyralid, amiprofos-methyl, amitrole, ammonium sulfamate, anilofos, anisuron, asulam, atraton, atrazine, azafenidin, azimsulfuron, aziprotryne, barban, BCPC, beflubutamid, benazolin, bencarbazone, benfluralin, benfuresate, bensulfuron, bensulide, bentazone, benzadox, benzfendizone, benzipram, benzobicyclon, benzofenap, benzofluor, benzoylprop, benzthiazuron, bicyclopyrone, bifenox, bilanafos, bispyribac, borax, bromacil, bromobonil, bromobutide, bromofenoxim, bromoxynil, brompyrazon, butachlor, butafenacil, butamifos, butenachlor, buthidazole, buthiuron, butralin, butroxydim, buturon, butylate, cacodylic acid, cafenstrole, calcium chlorate, calcium cyanamide, cambendichlor, carbasulam, carbetamide, carboxazole chlorprocarb, carfentrazone, CDEA, CEPC, chlomethoxyfen, chloramben, chloranocryl, chlorazifop, chlorazine, chlorbromuron, chlorbufam, chloreturon, chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol, chloridazon, chlorimuron, chlornitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorpropham, chlorsulfuron, chlorthal, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, cisanilide, clethodim, cliodinate, clodinafop, clofop, clomazone, clomeprop, cloprop, cloproxydim, clopyralid, cloransulam, CMA, copper sulfate, CPMF, CPPC, credazine, cresol, cumyluron, cyanatryn, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop, cyperquat, cyprazine, cyprazole, cypromid, daimuron, dalapon, dazomet, delachlor, desmedipham, desmetryn, di-allate, dicamba, dichlobenil, dichloralurea, dichlormate, dichlorprop, dichlorprop-P, diclofop, diclosulam, diethamquat, diethatyl, difenopenten, difenoxuron, difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimexano, dimidazon, dinitramine, dinofenate, dinoprop, dinosam, dinoseb, dinoterb, diphenamid, dipropetryn, diquat, disul, dithiopyr, diuron, DMPA, DNOC, DSMA, EBEP, eglinazine, endothal, epronaz, EPTC, erbon, esprocarb, ethalfluralin, ethametsulfuron, ethidimuron, ethiolate, ethofumesate, ethoxyfen, ethoxysulfuron, etinofen, etnipromid, etobenzanid, EXD, fenasulam, fenoprop, fenoxaprop, fenoxaprop-P, fenoxasulfone, fenteracol, fenthiaprop, fentrazamide, fenuron, ferrous sulfate, flamprop, flamprop-M, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazolate, flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenican, flufenpyr, flumetsulam, flumezin, flumiclorac, flumioxazin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen, fluoromidine, fluoronitrofen, fluothiuron, flupoxam, flupropacil, flupropanate, flupyrsulfuron, fluridone, fluorochloridone, fluoroxypyr, flurtamone, fluthiacet, fomesafen, foramsulfuron, fosamine, furyloxyfen, glufosinate, glufosinate-P, glyphosate, halosafen, halosulfuron, haloxydine, haloxyfop, haloxyfop-P, hexachloroacetone, hexaflurate, hexazinone, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, indanofan, indaziflam, iodobonil, iodomethane, iodosulfuron, ioxynil, ipazine, ipfencarbazone, iprymidam, isocarbamid, isocil, isomethiozin, isonoruron, isopolinate, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, karbutilate, ketospiradox, lactofen, lenacil, linuron, MAA, MAMA, MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, medinoterb, mefenacet, mefluidide, mesoprazine, mesosulfuron, mesotrione, metam, metamifop, metamitron, metazachlor, metazosulfuron, metflurazon, methabenzthiazuron, methalpropalin, methazole, methiobencarb, methiozolin, methiuron, methometon, methoprotryne, methyl bromide, methyl isothiocyanate, methyldymron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, molinate, monalide, monisouron, monochloroacetic acid, monolinuron, monuron, morfamquat, MSMA, naproanilide, napropamide, naptalam, neburon, nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen, norflurazon, noruron, OCH, orbencarb, ortho-dichlorobenzene, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon, oxasulfuron, oxaziclomefone, oxyfluorfen, parafluoron, paraquat, pebulate, pelargonic acid, pendimethalin, penoxsulam, pentachlorophenol, pentanochlor, pentoxazone, perfluidone, pethoxamid, phenisopham, phenmedipham, phenmedipham-ethyl, phenobenzuron, phenylmercury acetate, picloram, picolinafen, pinoxaden, piperophos, potassium arsenite, potassium azide, potassium cyanate, pretilachlor, primisulfuron, procyazine, prodiamine, profluazol, profluralin, profoxydim, proglinazine, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propyrisulfuron, propyzamide, prosulfalin, prosulfocarb, prosulfuron, proxan, prynachlor, pydanon, pyraclonil, pyraflufen, pyrasulfotole, pyrazolynate, pyrazosulfuron, pyrazoxyfen, pyribenzoxim, pyributicarb, pyriclor, pyridafol, pyridate, pyriftalid, pyriminobac, pyrimisulfan, pyrithiobac, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quinonamid, quizalofop, quizalofop-P, rhodethanil, rimsulfuron, saflufenacil, S-metolachlor, sebuthylazine, secbumeton, sethoxydim, siduron, simazine, simeton, simetryn, SMA, sodium arsenite, sodium azide, sodium chlorate, sulcotrione, sulfallate, sulfentrazone, sulfometuron, sulfosulfuron, sulfuric acid, sulglycapin, swep, TCA, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn, tetrafluoron, thenylchlor, thiazafluoron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone-methyl, thifensulfuron, thiobencarb, tiocarbazil, tioclorim, topramezone, tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam, tribenuron, tricamba, triclopyr, tridiphane, trietazine, trifloxysulfuron, trifluralin, triflusulfuron, trifop, trifopsime, trihydroxytriazine, trimeturon, tripropindan, tritac, tritosulfuron, vernolate, and xylachlor.
Another embodiment of the present disclosure is a method for the control or prevention of fungal attack. This method comprises applying to the soil, plant, roots, foliage, seed or locus of the fungus, or to a locus in which the infestation is to be prevented (for example applying to cereal or grape plants), a fungicidally effective amount of one or more of the compounds of Formula I. The compounds are suitable for treatment of various plants at fungicidal levels, while exhibiting low phytotoxicity. The compounds may be useful both in a protectant and/or an eradicant fashion.
The compounds have been found to have significant fungicidal effect particularly for agricultural use. Many of the compounds are particularly effective for use with agricultural crops and horticultural plants.
It will be understood by those in the art that the efficacy of the compound for the foregoing fungi establishes the general utility of the compounds as fungicides.
The compounds have broad ranges of activity against fungal pathogens. Exemplary pathogens may include, but are not limited to, causing agent of wheat leaf blotch (Mycosphaerella graminicola; impect stage: Septoria tritici), brown rust (Puccinia triticina), stripe rust (Puccinia striiformis), scab of apple (Venturia inaequalis), blister smut of maize (Ustilago maydis), powdery mildew of grapevine (Uncinula necator), leaf blotch of cereals (Rhynchosporium secalis), blast of rice (Magnaporthe grisea), downy mildew of cucurbits (Pseudoperonospora cubensis), rust of soybean (Phakopsora pachyrhizi), glume blotch of wheat (Leptosphaeria nodorum), powdery mildew of wheat (Blumeria graminis f. sp. tritici), powdery mildew of barley (Blumeria graminis f. sp. hordei), powdery mildew of cucurbits (Erysiphe cichoracearum), anthracnose of cucurbits (Glomerella lagenarium), leaf spot of beet (Cercospora beticola), early blight of eggplant (Alternaria solani), and net blotch of barley (Pyrenophora teres). The exact amount of the active material to be applied is dependent not only on the specific active material being applied, but also on the particular action desired, the fungal species to be controlled, and the stage of growth thereof, as well as the part of the plant or other product to be contacted with the compound. Thus, all the compounds, and formulations containing the same, may not be equally effective at similar concentrations or against the same fungal species.
The compounds are effective in use with plants in a disease-inhibiting and phytologically acceptable amount. The term “disease-inhibiting and phytologically acceptable amount” refers to an amount of a compound that kills or inhibits the plant disease for which control is desired, but is not significantly toxic to the plant. This amount will generally be from about 0.1 to about 1000 ppm (parts per million), with 1 to 500 ppm being preferred. The exact concentration of compound required varies with the fungal disease to be controlled, the type of formulation employed, the method of application, the particular plant species, climate conditions, and the like. A suitable application rate is typically in the range from about 0.10 to about 4 pounds/acre (about 0.01 to 0.45 grams per square meter, g/m2). Fungicidally effective amount of the compounds include amounts sufficient to kill or control true fungi, pseudo-fungi, and related organisms including water moulds.
Any range or desired value given herein may be extended or altered without losing the effects sought, as is apparent to the skilled person for an understanding of the teachings herein.
The compounds of Formula I may be made using well-known chemical procedures. Intermediates not specifically mentioned in this disclosure are either commercially available, may be made by routes disclosed in the chemical literature, or may be readily synthesized from commercial starting materials utilizing standard procedures.
General Schemes
The following schemes illustrate approaches to generating picolinamide compounds of Formula (I). It may be understood by those skilled in the art that R1 and R2 may be differentially substituted through sequential derivatizations, such as an arylation reaction followed by an allylation reaction. The following descriptions and examples are provided for illustrative purposes and should not be construed as limiting in terms of substituents or substitution patterns. The derivatizations that result in differential substitution at R1 and R2 are designated as “Derivatization Type”, wherein n=1 or 2. For example, “Arylation1” indicates that the first derivatization performed is an arylation reaction and “Allylation2” denotes that the derivatization being performed second in the sequence is an allylation reaction. Additionally, this convention is applied to the structures throughout the schemes as well. For example, the structure below indicates that R1 is an aryl substituent that was installed as the first derivatization of the diol, i.e. R1 and R2═H, and that R2 is an allyl substituent that was installed as the second derivatization of a mono-substituted alcohol, i.e. R1=aryl and R2═H.




Compounds of Formulas 1.6, 1.7, 1.8, 1.9, 1.10, and 1.11 (shown below), wherein R5 are previously defined within the scope of this disclosure, may be prepared as shown in Scheme 1. In step a of Scheme 1, treatment of a 3,4-dihydropyran of Formula 1.1, prepared as in Nicolaou, K. C. et al. J. Am. Chem. Soc., 2004, 126, 6234-6235, with ozone in the presence of a base, such as sodium bicarbonate (NaHCO3), in a mixture of a halogenated solvent such as dichloromethane (CH2Cl2) and an alcoholic solvent such as methanol (MeOH), followed by treatment with a biphasic mixture of an aqueous solution of a base, such as LiOH, and a polar aprotic solvent such as tetrahydrofuran (THF) provides the compound of Formula 1.2. In step b of Scheme 1, the compound of Formula 1.2 may be treated with an glide, such as that which is generated from methyltriphenyl phosphonium bromide and a base such as n-butyl lithium, to produce a compound of Formula 1.3. In step c of Scheme 1, the compound of Formula 1.3 may be protected as an ester, such as an acetate, by treating with an acylating agent such as acetyl chloride or acetic anhydride in the presence of an organic base, such as triethylamine (TEA), in a halogenated solvent, such as CH2Cl2, to afford a compound of Formula 1.4. In step d of Scheme 1, the compound of Formula 1.4 may be treated with an alkylborane reagent, such as 9-borabicyclo[3.3.1]nonane (9-BBN), in a polar aprotic solvent such as THF, at a temperature between ambient temperature and 50° C. Treatment of the resulting mixture between ambient temperature and 55° C. with an aqueous solution of a base, such as potassium phosphate, a brominated olefin, such as the compound of Formula 1.5, wherein R5 is tert-butoxy, prepared as in Singh, Janak et al. Organic Letters, 2003, 5(17), 3155-3158, and a catalyst, such as [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (PdCl2(dppf) affords the compound of Formula 1.6. In step e of Scheme 1, treatment of the compound of Formula 1.6 with hydrogen (15-200 psi) in the presence of a catalyst, such as 1,2-bis[(2S,5S)-2,5-diethyl-phospholano]benzene(1,5-cyclooctadiene)rhodium(I) trifluoromethanesulfonate ((S,S)-Et-DUPHOS-Rh), in an alcoholic solvent such as MeOH, afforded a compound of Formula 1.7. In step f of Scheme 1, treatment of the compound of Formula 1.7 with a base such as lithium hydroxide (LiOH) in a mixture of water and an alcoholic solvent such as MeOH produced a compound of Formula 1.8. In step g of Scheme 1, a solution of a compound of Formula 1.8 in a halogenated solvent such as CH2Cl2 or an aromatic solvent such as toluene may be added over a period of 4-12 hours (h) to a mixture of a base such as 4-dimethylaminopyridine (DMAP) and an anhydride such as 2-methyl-6-nitrobenzoic anhydride (MNBA) in either a halogenated solvent such as CH2Cl2 or an aromatic solvent such as toluene to generate a compound of Formula 1.9. In step h of Scheme 1, a compound of Formula 1.9 may be protected with a group such as a carbamate, for example a tert-butylcarbamate, by treating with an alkyl, alkylaryl, haloalkyl, or an aryl dicarbonate such as di-tert-butyl dicarbonate in the presence of a base, such as DMAP, in a polar aprotic solvent such as acetonitrile (CH3CN), to afford a compound of Formula 1.10. In step i of Scheme 1, treatment of a solution of a compound of Formula 1.10 in a solvent such as ethyl acetate (EtOAc) with hydrogen gas (15-55 psi) in the presence of a palladium catalyst, such as 5% or 10% w/w palladium on carbon (Pd/C), affords a compound of Formula 1.11.







Arylation(1) 
Phenoxy compounds of Formulas 2.1, 2.2, and 2.3, wherein R1, R2, and R5 are previously defined within the scope of this disclosure, may be prepared as shown in step a of Scheme 2. In step a, treatment of a bis-carbamate protected amine of Formula 1.11, such as the bis tert-butylcarbamate, wherein R1 and R2 are hydrogen, with a triarylbismuth reagent, prepared according to the methods described by Hassan, A. et. al. Organometallics 1996, 15, 5613-5621, Moiseev, D. V. et al. J. Organomet. Chem. 2005, 690, 3652-3663, or Sinclair, P. J. et al. Bioorg. Med. Chem. Lett. 1995, 5, 1035-1038, in the presence of a copper catalyst, for example diacetoxycopper, and an aromatic solvent such as toluene at ambient or an elevated temperature, such as 40° C., affords a mixture of the arylated products of Formulas 2.1, 2.2, and 2.3.




Allylation(1) 
Alkoxy compounds of Formulas 3.4, 3.5, and 3.6, wherein R1, R2, and R5 are previously defined within the scope of this disclosure, may be prepared as shown in steps a and b of Scheme 3. In step a, treatment of a bis-carbamate protected amine of Formula 1.11, such as the bis tert-butylcarbamate, wherein R1 and R2 are hydrogen, with an allyl carbonate, such as a tert-butyl (allyl) carbonate or a symmetric (allyl) carbonate, such as bis(2-methallyl) carbonate, in the presence of a palladium catalyst and ligand, for example tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3) and 1,1′-bis(diphenylphosphino)-ferrocene (dppf), in a polar aprotic solvent like THF at an elevated temperature, such as 60° C., affords a mixture of the allyloxy products of Formulas 3.1, 3.2, and 3.3. Subsequently, the allyloxy compounds may be reduced, as shown in step b, to the corresponding alkoxy compounds of Formulas 3.4, 3.5, and 3.6, wherein R1, R2, and R5 are previously defined, under standard catalytic hydrogenation conditions. For example, stirring solutions of compounds of Formulas 3.1, 3.2, or 3.3 in a solvent like EtOAc with a palladium catalyst, such as 5% or 10% w/w Pd/C, under an atmosphere of hydrogen affords the alkoxy compounds of Formulas 3.4, 3.5, and 3.6. In step c, mono-substituted compounds of Formulas 3.3 or 3.6 may be treated with an alkylating reagent, such as trimethyloxonium tetrafluoroborate, in the presence of a base, such as Proton Sponge®, in a solvent such as CH2Cl2 to afford the di-substituted compounds of Formula 3.7, wherein R1, R2, and R5 are as previously defined. Compounds of Formula 3.7, where R2 is allyl, may be subsequently reduced under the conditions previously disclosed in step b to afford compounds of Formula 3.5.




Acylation(1) 

Acyloxy compounds of Formula 4.1, wherein R1, R2, and R5 are previously defined herein, may be prepared as shown in step a of Scheme 4. In step a, treatment of a solution of a bis-carbamate protected amine of Formula 1.11, such as the bis tert-butylcarbamate, wherein R1 and R2 are hydrogen, with a base such as 4-dimethylaminopyridine (DMAP) in a solvent such as CH2Cl2, followed by treatment with an acid chloride affords the acyloxy compound of Formula 4.1.




Arylation(2) 

Disubstituted compounds of Formula 5.3 and 5.4, wherein R1, R2, and R5 are previously defined within the scope of this disclosure, may be prepared as illustrated in step a of Scheme 5. Arylation of a bis-carbamate protected amine, such as the bis tert-butylcarbamate, of the isomeric monosubstituted compounds of Formulas 5.1 and 5.2, wherein R2 is hydrogen and R1 is hydrogen respectively, may be accomplished using the copper catalyzed triarylbismuth conditions previously disclosed in step a of Scheme 2.




Allylation(2) 

Disubstituted compounds of Formula 6.3, 6.4, 6.5, and 6.6, wherein R1, R2, and R5 are previously defined within the scope of this disclosure, may be prepared as illustrated in steps a and b of Scheme 6. Allylation of a bis-carbamate protected amine, such as the bis tert-butylcarbamate, of the isomeric monosubstituted compounds of Formulas 6.1 and 6.2, wherein R2 is hydrogen and R1 is hydrogen respectively, may be accomplished using the palladium catalyzed allylation conditions previously disclosed in step a of Scheme 3 to give the disubstituted compounds of Formula 6.3 and 6.4, wherein R1, R2, and R5 are previously defined. Subsequent palladium catalyzed hydrogenation of compounds of Formulas 6.3 and 6.4, as previously disclosed in step b of Scheme 3, affords compounds of Formulas 6.5 and 6.6. Alternatively, disubstituted compounds of Formula 6.5 and 6.6, wherein R1, R2, and R5 are previously defined, can be obtained from monosubstituted compounds of Formulas 6.1 and 6.2, wherein R2 is hydrogen and R1 is hydrogen respectively, via direct alkylation as disclosed in step c of Scheme 3.




Acylation(2) 

Disubstituted compounds of Formulas 7.3 and 7.4, wherein R1, R2, and R5 are previously defined herein, may be prepared as illustrated in step a of Scheme 7. Acylation of a bis-carbamate protected amine, such as the bis tert-butylcarbamate, of the isomeric monosubstituted compounds of Formulas 7.1 and 7.2, wherein R2 is hydrogen and R1 is hydrogen respectively, may be accomplished by treating solutions of the compounds in CH2Cl2 with an organic base, such as pyridine, followed by treatment with an acid chloride to give the disubstituted compounds of Formulas 7.3 and 7.4, wherein R1, R2, and R5 are previously defined.




Conjugate Addition

Disubstituted compounds of Formulas 8.7 and 8.8, wherein R1, R2, and R5 are previously defined within the scope of this disclosure, may be prepared as illustrated in steps a, b, and c of Scheme 8. Addition of a bis-carbamate protected amine, such as the bis tert-butylcarbamate, of the isomeric monosubstituted compounds of Formulas 8.1 and 8.2, wherein R2 and R1 are hydrogen respectively, into conjugated alkynes, such as but-3-yn-2-one, may be accomplished by treating solutions of the compounds in a solvent such as CH2Cl2 with a catalytic amount of 1,4-diazabicyclo[2.2.2]octane (DABCO), followed by addition of the conjugated alkyne at a reduced temperature, for example 0° C., to afford mixtures of E and Z isomers of the conjugate addition products of Formulas 8.3 and 8.4, as shown in step a. Subjecting the olefinic compounds of Formulas 8.3 and 8.4 to the catalytic hydrogenation conditions previously disclosed in step b of Schemes 3, as shown in step b, affords the alkoxy-ketones of Formulas 8.5 and 8.6, wherein R1, R2 and R5 are previously defined within the scope of this application. Subsequent reduction of the ketones may be accomplished through treatment of the compounds of Formulas 8.5 or 8.6 in an alcohol, such as MeOH with a reducing agent, such as sodium borohydride (NaBH4). Alkylation of the resulting diastereomeric mixtures of the hydroxyl intermediates may be achieved by treating the alcohols with an amine base, such as 1,8-Bis(dimethylamino)naphthalene (Proton Sponge®), in a solvent such as CH2Cl2, followed by an alkylating agent, for example trimethyloxonium tetrafluoroborate, to give compounds of Formulas 8.7 and 8.8, as shown in step c of Scheme 8.




Deprotection and Amide Formation

Picolinamide compounds of Formula 9.3, wherein R1, R2, X, and Y are previously defined herein, may be prepared as illustrated in steps a and b of Scheme 9. Amine salts of Formula 9.2, may be prepared by treating a solution of a bis-carbamate protected amine of Formula 9.1, wherein R5 is tert-butoxy and R1 and R2 are previously defined within the scope of this disclosure, in a halogenated solvent, such as CH2Cl2 or chloroform (CHCl3), or neat, with a solution of a mineral acid, for example hydrogen chloride (HCl) in a solvent such as dioxane, to give the HCl salts of compounds of Formula 9.2, as shown in step a. In step b, solutions of compounds of Formula 9.2, wherein R1 and R2 are previously defined, are treated with 3-methoxy-4-hydroxypicolinic acid and an excess of an organic base, such as diisopropylethyl amine or N-methylmorpholine, followed by a peptide coupling reagent, for example benzotriazol-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate (PyBOP) or (dimethylamino)-N,N-dimethyl(3H-[1,2,3]triazolo[4,5-b]pyridin-3-yloxy)methaniminium hexafluorophosphate (HATU), in a halogenated solvent such as CH2Cl2 to give compounds of Formula 9.3, wherein X is hydrogen, Y is Q, and R1 and R2 are as defined within the scope of this disclosure.




Hydroxypyridine Substitution

Picolinamide compounds of Formula 10.2, wherein R1, R2, and R3 are previously defined herein, may be prepared as illustrated in methods a or b of Scheme 10. Treating picolinamide compounds of Formula 10.1, wherein R3 is hydrogen and R1 and R2 are previously defined, with an organic base such as TEA and a catalyst, such as DMAP, in a halogenated solvent like CH2Cl2, followed by an acid chloride, for example acetyl chloride or 3-methoxypropanoyl chloride, affords compounds of Formula 10.2, as shown in method a. Alternatively, method b illustrates that treating picolinamide compounds of Formula 10.1, wherein R3 is hydrogen and R1 and R2 are previously defined, with a carbonate base, such as sodium or potassium carbonate (Na2CO3 or K2CO3), with or without the addition of a catalytic amount of sodium iodide (NaI) in a solvent like acetone, followed by an alkyl halide, such as bromomethylacetate, chloromethylisobutyrate, or chloromethyl 2-ethoxyacetate (as prepared in Meyer, K. G.; Bravo-Altamirano, K.; Renga, J. M.; Herrick, J.; Nugent, B. M.; Boebel, T. A.; Li, F.; Wang, N. X.; Owen, W. J.; Graupner, P. R.; Yao, C.; Heemstra, R. J. Preparation of N-macrocyclyl picolinamides as fungicides. US 20130296375, Nov. 7, 2013) also affords picolinamide compounds of Formula 10.2, wherein R1, R2, and R3 are previously defined within the scope of this disclosure.




Acetal Formation

Acetal compounds of Formula 11.0, wherein R5 is previously defined within the scope of this disclosure and R1 is aryl, alkyl or alkenyl, may be prepared as shown in Scheme 11. In Scheme 11, treatment of a bis-carbamate protected amine of Formula 1.11, such as the bis tert-butylcarbamate, wherein R1 and R2 are hydrogen and R5 is tert-butoxy, with an aldehyde, such as benzaldehyde, in the present of an acid catalyst, for example p-toluenesulfonic acid, and a dessicant, such as magnesium sulfate (MgSO4), in a solvent such as CH2Cl2 or toluene at ambient temperature, affords the acetal product of Formula 11.0, where and R1 and R5 are as defined above.




Aryl Functionalization

Functionalized compounds of Formula 12.2, wherein R1 is aryl, R2 is alkyl, and R5 is as previously defined within the scope of this disclosure, and compounds of Formula 12.5, wherein R1 is alkyl, R2 is aryl, and R5 is as previously defined within the scope of this disclosure, may be prepared as illustrated in Scheme 12, steps a and b. In step a, treatment of the aryl ethers of Formulas 12.0 and 12.3, wherein R1, R2, and R5 are as defined above, with a halogenating agent, such as N-bromosuccinimide (NBS), in an aprotic solvent such as CH2Cl2 at ambient temperature affords the halogenated compounds of Formulas 12.1 and 12.4, wherein R1, R2, and R5 are as defined above. In step b, the halogenated aryl ethers of Formulas 12.1 and 12.4, wherein R1, R2, and R5 are as defined above, may be cross-coupled with a boronic acid or boronate ester, such as phenyl boronic acid, in the presence of a base, such as Na2CO3 and a palladium catalyst, such as tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4), in a mixed solvent system, for example dioxane/water, at an elevated temperature, such as 80° C., to give compounds of Formulas 12.2 and 12.5, wherein R1, R2, and R5 are as defined above and R4 is alkyl, aryl, or alkenyl.




The following examples are presented to illustrate the various aspects of the compounds of the present disclosure and should not be construed as limitations to the claims.
EXAMPLES
Example 1
Preparation of (2S,3R,4S)-2-methyl-3,4-dihydro-2H-pyran-3,4-diol (C1)




To a solution of (2S,3S,4S)-2-methyl-3,4-dihydro-2H-pyran-3,4-diyl diacetate (32.10 grams (g), 150 millimole (mmol)) in MeOH (150 milliliters (mL)) was added K2CO3 (2.07 g, 15.0 mmol). This mixture was stirred for 16 h at 20° C. The resulting yellow solution was filtered through a plug of silica gel, 6 centimeters (cm)×2 cm, that was flushed with EtOAc (500 mL). The solvent was concentrated to provide (2S,3R,4S)-2-methyl-3,4-dihydro-2H-pyran-3,4-diol (19.9 g, 102% yield with 95% purity resulting in 97% corrected yield) as a yellow solid, which was used without further purification: 1H NMR (400 MHz, CDCl3) δ 6.31 (dd, J=6.0, 1.6 Hz, 1H), 4.70 (dd, J=6.0, 2.1 Hz, 1H), 4.21 (dt, J=7.4, 1.9 Hz, 1H), 3.85 (dq, J=9.9, 6.3 Hz, 1H), 3.41 (dd, J=9.9, 7.4 Hz, 1H), 1.38 (d, J=6.3 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 144.82, 102.65, 75.64, 74.36, 70.34, 17.09; EIMS m/z 130 ([M+]).
Example 2
Preparation of (2S,3S,4S)-3,4-bis(benzyloxy)-2-methyl-3,4-dihydro-2H-pyran (C2)




Sodium hydride, 60% dispersion in mineral oil, (NaH; 14.68 g, 367 mmol) was added to a 1 liter (L), 3-neck round bottomed flask under nitrogen. The NaH dispersion was washed with hexanes (100 mL and 50 mL) and then suspended in anhydrous N,N-dimethylformamide (DMF; 230 mL) and cooled to 0° C. in an ice water bath. The flask was fitted with a 125 mL addition funnel that was then charged with (2S,3R,4S)-2-methyl-3,4-dihydro-2H-pyran-3,4-diol (19.9 g, 153 mmol) as a solution in anhydrous DMF (70 mL). The diol solution was added to the NaH suspension dropwise with modification of the flow rate to mitigate the reaction rate and frothing. The addition took a total of 15 minutes (min). This mixture was then stirred at 0° C. for a further 30 min. The addition funnel was charged with benzyl bromide (40.0 ml, 336 mmol) that was added dropwise over 10 min. The mixture was then allowed to slowly warm to 20° C. over 16 h. The reaction was quenched by the slow and careful dropwise addition of saturated aqueous ammonium chloride (NH4Cl) solution (20 mL), poured into methyl-t-butyl ether (MTBE; 900 mL), washed with water (600 mL) and saturated aqueous sodium chloride (NaCl, brine) solution (300 mL), dried over MgSO4, filtered, and concentrated to provide a yellow oil (49.32 g, 99%; adjusted for 22 mol % residual DMF): IR (thin film) 3063, 3030, 2975, 2870, 1645, 1496, 1453, 1236, 1099, 1054, 733, 695 cm−1; 1H NMR (400 MHz, CDCl3) δ 7.54-7.26 (m, 10H), 6.36 (dd, J=6.1, 1.1 Hz, 1H), 4.95-4.80 (m, 2H), 4.80-4.62 (m, 2H), 4.57 (d, J=11.7 Hz, 1H), 4.21 (dt, J=6.5, 1.9 Hz, 1H), 3.95 (dq, J=8.9, 6.4 Hz, 1H), 3.49 (dd, J=8.9, 6.5 Hz, 1H), 1.38 (d, J=6.4 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 144.82, 138.44, 138.29, 128.45, 128.00, 127.79, 127.67, 100.17, 79.55, 74.11, 74.00, 70.58, 17.54.
Example 3
Preparation of (3R,4S,5S)-3,4-bis(benzyloxy)-5-methyltetrahydrofuran-2-ol (C3)




To a solution of (2S,3S,4S)-3,4-bis(benzyloxy)-2-methyl-3,4-dihydro-2H-pyran (41.8 g, 135 mmol) in CH2Cl2 (405 mL) and MeOH (50 mL) was added NaHCO3 (1.13 g, 13.5 mmol). This mixture was cooled to −78° C. (dry ice/acetone bath) and a stream of ozone was passed through the reaction until the solution took on a blue color (2 h). Oxygen was passed through until the blue color disappeared (10 min) and then dimethyl sulfide (19.9 ml, 269 mmol) was added. The solution was warmed to 20° C. and stirred overnight. The reaction was filtered through a plug of Celite® and concentrated to provide an oil. This oil was dissolved in THF (300 mL), a solution of LiOH (9.68 g, 404 mmol) in water (150 mL) was added, and the mixture was stirred vigorously at 20° C. for 2.5 h. The phases were separated and the aqueous phase was extracted with EtOAc (2×100 mL). The combined organic extracts were washed with saturated aqueous NaCl solution (100 mL), dried over MgSO4, filtered, and concentrated to provide a yellow oil. Purification by automated silica gel column chromatography (5→30% acetone/hexanes) provided (3R,4S,5S)-3,4-bis(benzyloxy)-5-methyltetrahydrofuran-2-ol (34.1 g, 80%) as a yellow oil. The product exists as an inseparable mixture of isomers: IR (neat film) 3402, 3031, 2934, 1658, 1496, 1454, 1367, 1105, 1059, 989, 736, 697 cm−1; 1H NMR (400 MHz, CDCl3) δ 7.45-7.25 (m, 42H), 5.37 (d, J=6.7 Hz, 3H), 5.30 (dd, J=8.5, 4.3 Hz, 1H), 4.66 (dd, J=5.3, 2.4 Hz, 1H), 4.64-4.47 (m, 16H), 4.35 (qd, J=6.4, 4.9 Hz, 3H), 3.98 (dd, J=2.5, 0.9 Hz, 3H), 3.97-3.89 (m, 2H), 3.80 (d, J=8.5 Hz, 1H), 3.77-3.72 (m, 1H), 3.66 (ddd, J=4.8, 2.5, 0.7 Hz, 3H), 3.40 (d, J=6.7 Hz, 3H), 1.34 (d, J=6.4 Hz, 3H), 1.31 (d, J=6.4 Hz, 9H); 13C NMR (101 MHz, CDCl3) δ 137.73, 137.48, 137.42, 137.05, 128.63, 128.57, 128.52, 128.50, 128.24, 128.08, 127.98, 127.94, 127.91, 127.82, 127.81, 127.69, 127.00, 100.88, 95.90, 87.42, 87.31, 86.68, 83.14, 78.65, 76.43, 72.67, 72.19, 71.97, 65.37, 20.84, 19.38.
Example 4
Preparation of (2S,3S,4S)-3,4-bis(benzyloxy)hex-5-en-2-ol (C4)




To a suspension of methyltriphenylphosphonium bromide (75.0 g, 211 mmol) in anhydrous THF (400 ml) under nitrogen at 0° C. (ice water bath) in a 1000 mL, 3-neck round bottom flask was added a 2.5 molar (M) solution of n-butyllithium in hexane (n-BuLi; 81.0 ml, 202 mmol) dropwise via syringe, keeping the internal temperature below 15° C. The resulting red solution was stirred at 0° C. for 45 min and then cooled to −78° C. (dry ice/acetone bath). A solution of (3R,4S,5S)-3,4-bis(benzyloxy)-5-methyltetrahydrofuran-2-ol (26.5 g, 84 mmol) in anhydrous THF (20 mL) was added via syringe and the solution was stirred for 30 min at −78° C., and then removed from the cold bath and stirred at 20° C. for 16 h. The reaction was quenched with saturated aqueous NH4Cl solution (200 mL), diluted with water (200 mL) and diethyl ether (Et2O; 400 mL). The phases were separated and the aqueous phase was extracted with Et2O (2×200 mL). The combined organic phases were dried over MgSO4, filtered, and concentrated to provide an orange oil. Purification by automated silica gel column chromatography (220% acetone/hexanes) provided (2S,3S,4S)-3,4-bis(benzyloxy)hex-5-en-2-ol (20.23 g, 77%) as a yellow oil: 1H NMR (400 MHz, CDCl3) δ 7.45-7.25 (m, 10H), 5.92 (ddd, J=17.2, 10.6, 7.6 Hz, 1H), 5.44-5.25 (m, 2H), 4.75 (d, J=11.6 Hz, 1H), 4.70-4.54 (m, 2H), 4.38 (d, J=11.8 Hz, 1H), 4.12-3.99 (m, 1H), 3.91 (h, J=6.3 Hz, 1H), 3.50-3.35 (m, 1H), 2.73 (d, J=5.9 Hz, 1H), 1.17 (d, J=6.3 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 138.31, 137.79, 134.47, 128.46, 128.37, 127.95, 127.94, 127.79, 127.72, 119.27, 83.70, 81.18, 74.07, 70.61, 67.37, 18.90; ESIMS m/z 313.5 ([M+Na]+).
Example 5
Preparation of (2S,3S,4S)-3,4-bis(benzyloxy)hex-5-en-2-yl acetate (C5)




To a solution of (2S,3S,4S)-3,4-bis(benzyloxy)hex-5-en-2-ol (800 milligrams (mg), 2.56 mmol) in CH2Cl2 (10 mL) at room temperature was added TEA (1.07 ml, 7.68 mmol), acetic anhydride (0.48 ml, 5.12 mmol) and DMAP (62.6 mg, 0.512 mmol). The reaction mixture was stirred at room temperature for 2 h, concentrated and purified by column chromatography on SiO2 (0→20% EtOAc/hexanes) to yield the title compound as a colorless oil (891 mg, 98%): 1H NMR (400 MHz, CDCl3) δ 7.41-7.23 (m, 10H), 5.84 (ddd, J=17.2, 10.4, 8.2 Hz, 1H), 5.38-5.26 (m, 2H), 5.02 (qd, J=6.5, 3.7 Hz, 1H), 4.83-4.67 (m, 2H), 4.61 (d, J=11.8 Hz, 1H), 4.37 (d, J=11.8 Hz, 1H), 3.84 (ddt, J=8.0, 6.3, 0.8 Hz, 1H), 3.63 (dd, J=6.3, 3.7 Hz, 1H), 1.91 (s, 3H), 1.26 (d, J=6.5 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 170.19, 138.64, 138.30, 135.07, 128.33, 128.25, 128.08, 127.94, 127.58, 127.52, 119.42, 82.90, 81.86, 74.98, 71.03, 70.48, 21.32, 14.75; ESIMS m/z 377.3 ([M+Na]+).
Example 6
Preparation of (6S,7S,8S,Z)-methyl 8-acetoxy-6,7-bis(benzyloxy)-2-((tert-butoxycarbonyl)amino)non-2-enoate (C6)




To a solution of (2S,3S,4S)-3,4-bis(benzyloxy)oct-7-en-2-yl acetate (931 mg, 2.63 mmol) in THF (2 mL) was added 9-BBN (0.5 M solution in THF, 6.82 mL, 3.41 mmol). The reaction mixture was stirred at room temperature for 30 min, then warmed to 50° C. and stirred for 2 h. After the reaction mixture was cooled to room temperature, an aqueous solution of potassium phosphate (K3PO4; 3 M, 1.75 mL, 5.25 mmol), a solution of (Z)-methyl 3-bromo-2-((tert-butoxycarbonyl)amino)acrylate (736 mg, 2.63 mmol) in DMF (9 mL, degassed), and PdCl2(dppf) (96 mg, 0.13 mmol) was added. The reaction mixture was heated to 55° C. and stirred overnight, and then quenched with saturated aqueous NaHCO3 and extracted with Et2O. The combined organic phase was dried over sodium sulfate (Na2SO4), filtered, concentrated, and purified by column chromatography on SiO2 (0→30% EtOAc/hexanes) to yield the title compound as a light yellow oil (1.26 g, 86%): IR (thin film) 3341, 2930, 1717, 1367, 1241 cm−1; 1H NMR (400 MHz, CDCl3) δ 7.43-7.26 (m, 10H), 6.48 (t, J=7.3 Hz, 1H), 6.03 (s, 1H), 5.08 (qd, J=6.5, 3.1 Hz, 1H), 4.77-4.58 (m, 3H), 4.49 (d, J=11.2 Hz, 1H), 3.76 (s, 3H), 3.64 (dd, J=6.1, 3.1 Hz, 1H), 3.44 (ddd, J=7.9, 6.0, 4.2 Hz, 1H), 2.43-2.29 (m, 1H), 2.29-2.16 (m, 1H), 1.98 (s, 3H), 1.85-1.61 (m, 2H), 1.44 (s, 9H), 1.31 (d, J=6.5 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 170.32, 165.29, 153.24, 138.41, 138.31, 135.67, 128.33, 128.04, 127.98, 127.68, 127.62, 81.82, 80.45, 79.30, 74.33, 73.15, 71.22, 70.56, 52.29, 29.54, 28.18, 24.66, 21.32, 15.09; HRMS-ESI (m/z) [M+H]+ calcd for C31H42NO8, 556.2905; found, 556.2903.
Example 7
Preparation of (2S,6S,7S,8S)-methyl-8-acetoxy-6,7-bis(benzyloxy)-2-((tert-butoxycarbonyl)amino)nonanoate (C7)




A solution of (6S,7S,8S,Z)-methyl 8-acetoxy-6,7-bis(benzyloxy)-2-((tert-butoxycarbonyl)amino)non-2-enoate (120 mg, 0.216 mmol) in anhydrous MeOH (4.3 mL) was purged with N2 for 15 min in a 250 mL stainless steel bomb. To the solution was added 1,2-bis[(2S,5S)-2,5-diethyl-phospholano]benzene(1,5-cyclooctadiene)rhodium(I) trifluoromethanesulfonate ((S,S)-Et-DUPHOS-Rh; 1.56 mg, 2.16 micromole (μmol)), and the vessel was sealed, purged twice with hydrogen (H2; 200 psi), and then pressurized to 200 psi with H2 and stirred at room temperature overnight. The reaction was concentrated and purified by column chromatography on SiO2 (0→30% EtOAc/hexanes) to yield the title compound as a colorless oil (110 mg, 91%): 1H NMR (400 MHz, CDCl3) δ 7.39-7.23 (m, 10H), 5.10-5.04 (m, 1H), 4.97 (d, J=8.4 Hz, 1H), 4.73 (d, J=11.6 Hz, 1H), 4.65 (d, J=7.7 Hz, 1H), 4.62 (d, J=7.4 Hz, 1H), 4.50 (d, J=11.4 Hz, 1H), 4.32-4.20 (m, 1H), 3.70 (s, 3H), 3.61 (dd, J=6.0, 3.1 Hz, 1H), 3.43-3.39 (m, 1H), 1.98 (s, 3H), 1.79-1.66 (m, 1H), 1.64-1.47 (m, 4H), 1.45 (s, 9H), 1.31 (d, J=6.5 Hz, 3H), 1.29-1.20 (m, 1H); 13C NMR (101 MHz, CDCl3) δ 173.27, 170.24, 155.35, 138.51, 138.45, 128.33, 128.05, 128.01, 127.67, 127.63, 81.89, 79.82, 79.39, 74.30, 73.07, 71.28, 53.33, 52.21, 32.68, 30.52, 28.34, 21.34, 15.13; ESIMS m/z 580.4 ([M+Na]+).
Example 8
Preparation of (2S,6S,7S,8S)-6,7-bis(benzyloxy)-2-((tert-butoxycarbonyl)amino)-8-hydroxynonanoic acid (C8)




To a solution of (2S,6S,7S,8S)-methyl 8-acetoxy-6,7-bis(benzyloxy)-2-((tert-butoxycarbonyl)amino)nonanoate (110 mg, 0.20 mmol) in MeOH (2 mL) and water (2 mL) at room temperature was added LiOH.H2O (33.1 mg, 0.789 mmol). The reaction mixture was stirred at room temperature for 3 h, quenched with 1 Normal (N) hydrochloric acid, and extracted with EtOAc. The combined organic phases were washed with saturated aqueous NaHCO3, dried over Na2SO4, filtered, and concentrated to yield the title compound as a colorless oil (96 mg, 97%): IR (thin film) 3409, 2929, 1686, 1588; 1H NMR (400 MHz, CDCl3) δ 7.33-7.21 (m, 10H), 5.40 (s, 1H), 4.56-4.48 (m, 4H), 3.96-3.81 (m, 2H), 3.57-3.51 (m, 1H), 3.31-3.23 (m, 1H), 1.81-1.41 (m, 6H), 1.37 (s, 9H), 1.19 (d, J=6.2 Hz, 3H); ESIMS m/z 524.4 ([M+Na]+).
Example 9
Preparation of tert-butyl ((3S,7S,8S,9S)-7,8-bis(benzyloxy)-9-methyl-2-oxooxonan-3-yl)carbamate (C9)




To a solution of DMAP (137 mg, 1.12 mmol) and MNBA (129 mg, 0.375 mmol) in CH2Cl2 (30 mL) at room temperature was added a solution of (2S,6S,7S,8S)-6,7-bis(benzyloxy)-2-((tert-butoxycarbonyl)amino)-8-hydroxynonanoic acid (94 mg, 0.19 mmol) in CH2Cl2 (8 mL) over 4 h via syringe pump. The reaction mixture was stirred overnight, concentrated and purified by column chromatography on SiO2 (0→20%, EtOAc/hexanes) to yield the title compound as a colorless oil (71 mg, 78%): 1H NMR (400 MHz, CDCl3) δ 7.41-7.26 (m, 10H), 5.03 (d, J=8.3 Hz, 1H), 4.88 (d, J=10.8 Hz, 1H), 4.85-4.77 (m, 1H), 4.68 (d, J=10.8 Hz, 1H), 4.61 (d, J=11.4 Hz, 1H), 4.48 (d, J=11.4 Hz, 1H), 4.20 (dt, J=10.9, 7.7 Hz, 1H), 3.67-3.57 (m, 2H), 2.26 (dt, J=13.6, 6.7 Hz, 1H), 2.21-2.09 (m, 1H), 1.77-1.60 (m, 2H), 1.44 (s, 9H), 1.41 (d, J=6.4 Hz, 3H), 1.23-1.11 (m, 1H), 0.99-0.87 (m, 1H); 13C NMR (101 MHz, CDCl3) δ 173.15, 154.91, 138.40, 138.31, 128.39, 128.37, 127.94, 127.80, 127.71, 127.64, 83.90, 83.70, 79.91, 75.77, 72.76, 71.20, 52.76, 33.88, 28.32, 28.00, 18.28, 18.10; ESIMS m/z 506.3 ([M+Na]+).
Example 10
Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-7,8-dibenzyloxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (C10)




A solution of tert-butyl ((3S,7S,8S,9S)-7,8-bis(benzyloxy)-9-methyl-2-oxooxonan-3-yl)carbamate (150 mg, 0.31 mmol), DMAP (19.0 mg, 0.155 mmol) and di-tert-butyl dicarbonate (271 mg, 1.24 mmol) in CH3CN (2.1 mL) was stirred at room temperature for 18 h, concentrated, and purified by column chromatography on SiO2 (0→15% EtOAc/hexanes) to yield the title compound (76 mg, 42%) as a colorless oil along with recovered starting material (72 mg, 48%) as a colorless oil: 1H NMR (400 MHz, CDCl3) δ 7.35-7.27 (m, 10H), 4.88 (d, J=10.9 Hz, 1H), 4.83 (dd, J=10.4, 8.0 Hz, 1H), 4.75-4.59 (m, 3H), 4.49 (d, J=11.4 Hz, 1H), 3.69-3.57 (m, 2H), 2.42-2.33 (m, 1H), 2.24-2.14 (m, 1H), 2.08-2.00 (m, 1H), 1.79-1.65 (m, 2H), 1.51 (s, 18H), 1.41 (d, J=6.3 Hz, 3H), 1.01 (ddt, J=16.0, 7.7, 1.8 Hz, 1H); 13C NMR (101 MHz, CDCl3) δ 170.86, 152.91, 138.52, 138.41, 128.39, 128.36, 127.95, 127.83, 127.68, 127.60, 84.08, 83.59, 82.71, 75.65, 72.95, 71.21, 57.43, 30.55, 28.50, 27.99, 19.28, 18.23; ESIMS m/z 606.4 ([M+Na]+).
Example 11
Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7,8-dihydroxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (F1)




A mixture of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-7,8-dibenzyloxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (66.0 mg, 0.113 mmol) and Pd/C (5% w/w Pd, 24.1 mg, 0.011 mmol) in EtOAc (2.3 mL) was stirred under an H2 balloon at room temperature for 7 h. The reaction mixture was filtered through Celite®, and concentrated to yield the title compound (44.0 mg, 96%) as a colorless oil: 1H NMR (400 MHz, CDCl3) δ 4.83 (dd, J=10.1, 7.3 Hz, 1H), 4.72 (dq, J=9.1, 6.3 Hz, 1H), 3.58-3.42 (m, 2H), 2.84 (s, 1H), 2.45 (s, 1H), 2.35 (dtd, J=13.8, 9.8, 2.2 Hz, 1H), 2.14-2.02 (m, 1H), 1.96-1.67 (m, 3H), 1.51 (s, 18H), 1.42 (d, J=6.3 Hz, 3H), 1.31-1.21 (m, 1H); 13C NMR (101 MHz, CDCl3) δ 170.77, 152.91, 82.81, 76.85, 73.86, 73.18, 57.69, 35.34, 30.93, 27.98, 20.03, 18.06; ESIMS m/z 426.3 ([M+Na]+).
Example 12
Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7-hydroxy-9-methyl-2-oxo-8-phenoxy-oxonan-3-yl]carbamate (C11)




A solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7,8-dihydroxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (1.845 g, 4.57 mmol), triphenylbismuth diacetate (3.06 g, 5.49 mmol) and diacetoxycopper (0.166 g, 0.915 mmol) in toluene (18.3 ml) was stirred at 40° C. for 1 h. The reaction mixture was filtered thru Celite®, the pad washed with toluene (2×40 mL), and the filtrate concentrated to yield 2.3 g light blue foam. Purification by column chromatography (SiO2, 0→20% EtOAc/hexanes) yielded the title compound as a white foam (1.15 g, 52%), along with the 7-substituted and 7,8-disubstituted products: 1H NMR (400 MHz, CDCl3) δ 7.33-7.24 (m, 2H), 7.03 (d, J=7.9 Hz, 2H), 6.98 (t, J=7.3 Hz, 1H), 4.96-4.80 (m, 2H), 4.29 (dd, J=9.4, 7.9 Hz, 1H), 3.86 (t, J=6.7 Hz, 1H), 2.47-2.27 (m, 2H), 2.15-1.95 (m, 2H), 1.91-1.71 (m, 2H), 1.59-1.40 (m, 19H), 1.31 (d, J=6.4 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 170.73, 159.42, 152.85, 129.69, 121.92, 116.27, 83.73, 82.78, 73.98, 72.46, 57.56, 33.41, 30.90, 27.98, 19.79, 18.31; HRMS-ESI (m/z) [M+Na]+ calcd for C25H37NNaO8, 502.2411; found, 502.2344.
The following compounds were prepared and isolated using the appropriately substituted triphenylbismuth diacetate reagents and the methodology described in Example 12:
tert-Butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-hydroxy-9-methyl-2-oxo-7-phenoxy-oxonan-3-yl]carbamate (C12)




Isolated as a white foam (520 mg, 24%): 1H NMR (400 MHz, CDCl3) δ 7.35-7.27 (m, 2H), 7.03-6.95 (m, 1H), 6.92 (dd, J=8.7, 1.0 Hz, 2H), 4.95 (t, J=8.5 Hz, 1H), 4.84 (dq, J=9.6, 6.3 Hz, 1H), 4.24-4.12 (m, 1H), 3.86 (ddd, J=9.9, 7.8, 2.4 Hz, 1H), 2.63 (d, J=2.5 Hz, 1H), 2.38-2.20 (m, 1H), 2.13-1.98 (m, 2H), 1.89 (tt, J=11.1, 5.6 Hz, 1H), 1.65-1.54 (m, 2H), 1.51 (s, 18H), 1.47 (d, J=6.3 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 170.56, 157.12, 152.90, 129.63, 121.65, 116.60, 82.78, 82.32, 75.72, 72.93, 57.26, 31.06, 30.37, 27.98, 20.17, 18.19; HRMS-ESI (m/z) [M+Na]+ calcd for C25H37NNaO8, 502.2411; found, 502.2399.
tert-Butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-2-oxo-7,8-diphenoxy-oxonan-3-yl]carbamate (C13)




Isolated as a white solid (172 mg, 7%): 1H NMR (400 MHz, CDCl3) δ 7.30-7.14 (m, 4H), 7.04 (dd, J=8.8, 1.0 Hz, 2H), 6.97-6.86 (m, 2H), 6.86-6.77 (m, 2H), 4.98 (dd, J=9.5, 6.4 Hz, 1H), 4.91 (dd, J=10.0, 8.3 Hz, 1H), 4.62 (dd, J=9.5, 7.4 Hz, 1H), 4.52 (ddd, J=7.1, 5.2, 1.6 Hz, 1H), 2.46-2.18 (m, 2H), 2.08 (dd, J=13.5, 6.8 Hz, 1H), 1.91 (dt, J=13.0, 7.3 Hz, 1H), 1.72 (m, H), 1.52 (s, 18H), 1.41 (d, J=6.4 Hz, 3H), 1.20 (dt, J=7.7, 1.8 Hz, 1H); 13C NMR (101 MHz, CDCl3) δ 170.71, 159.55, 157.64, 152.85, 129.39, 129.37, 121.54, 121.35, 116.72, 116.57, 82.81, 82.37, 82.21, 72.57, 57.25, 30.54, 28.98, 27.99, 19.32, 18.32; ESIMS m/z 578.8 ([M+Na]+).
tert-Butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-8-(4-fluorophenoxy)-7-hydroxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (C14)




Isolated as a colorless oil (150 mg, 0.30 mmol, 61%): 1H NMR (400 MHz, CDCl3) δ 7.04-6.90 (m, 4H), 4.93-4.82 (m, 2H), 4.17 (dd, J=9.4, 7.9 Hz, 1H), 3.86 (ddd, J=8.1, 6.1, 2.4 Hz, 1H), 2.40 (dtd, J=13.7, 9.9, 3.5 Hz, 2H), 2.16-1.94 (m, 2H), 1.82 (dd, J=6.1, 3.1 Hz, 2H), 1.52 (s, 18H), 1.49-1.41 (m, 1H), 1.31 (d, J=6.4 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 170.69, 157.76 (d, J=240.0 Hz), 155.62 (d, J=2.3 Hz), 152.85, 117.54 (d, J=8.0 Hz), 116.04 (d, J=23.2 Hz), 84.90, 82.82, 73.96, 72.30, 57.53, 33.52, 30.86, 27.97, 19.78, 18.35; ESIMS m/z 498.3 [(M+H)+].
Example 12A
Preparation of [(3S,7S,8S,9S)-9-methyl-2-oxo-7,8-diphenoxy-oxonan-3-yl]ammonium chloride (F2)




A solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-2-oxo-7,8-diphenoxy-oxonan-3-yl]carbamate (650 mg, 1.17 mmol) and HCl (4M in dioxane; 5.85 mL, 23.4 mmol) in CHCl3 (6 mL) was stirred at 23° C. for 1.5 h. The solution was concentrated to yield the title compound as a white foam (458 mg, 100%), which was used without further purification.
Example 12B
Step 1: Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-7-(2-methylallyloxy)-2-oxo-8-phenoxy-oxonan-3-yl]carbamate (C15)




A solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7-hydroxy-9-methyl-2-oxo-8-phenoxy-oxonan-3-yl]carbamate (1.075 g, 2.24 mmol), tert-butyl (2-methylallyl) carbonate (1.158 g, 6.70 mmol), dppf (0.025 g, 0.045 mmol) and Pd2(dba)3 (0.021 g, 0.022 mmol) in degassed THF (11.2 ml) was heated to 60° C. for 1.5 h. The solution was cooled to room temperature and purified by column chromatography (SiO2; 0→5% EtOAc/Hex) to yield the title compound (1.0 g, 84%) as a white solid: 1H NMR (400 MHz, CDCl3) δ 7.34-7.17 (m, 2H), 7.09-7.02 (m, 2H), 6.98-6.90 (m, 1H), 4.94-4.72 (m, 4H), 4.43 (dd, J=9.6, 7.4 Hz, 1H), 3.91 (d, 1H), 3.79 (d, 1H), 3.62 (ddd, J=7.0, 5.1, 1.7 Hz, 1H), 2.47-2.34 (m, 1H), 2.25-2.13 (m, 1H), 2.11-2.01 (m, 1H), 1.88-1.63 (m, 2H), 1.56 (s, 3H), 1.52 (s, 18H), 1.33 (d, J=6.4 Hz, 3H), 1.07 (dd, J=16.0, 7.7 Hz, 1H); 13C NMR (101 MHz, CDCl3) δ 170.80, 159.58, 152.86, 142.36, 129.36, 121.24, 116.29, 112.34, 82.72, 82.53, 82.06, 73.50, 72.76, 57.39, 30.56, 28.61, 27.98, 19.40, 19.29, 18.19; HRMS-ESI (m/z) [M+Na]+ calcd for C29H43NNaO8, 556.2881; found, 556.2873.
The following compounds were prepared and isolated using the methodology described in Example 12B, Step 1:
tert-Butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-8-(2-methylallyloxy)-2-oxo-7-phenoxy-oxonan-3-yl]carbamate (C16)




Isolated as a white solid (448 mg; 85%): 1H NMR (400 MHz, CDCl3) δ 7.30-7.23 (m, 2H), 6.99-6.88 (m, 3H), 4.94-4.72 (m, 4H), 4.46-4.35 (m, 1H), 4.22-4.16 (m, 1H), 4.03 (d, J=11.6 Hz, 1H), 3.67 (dd, J=9.7, 7.1 Hz, 1H), 2.38-2.25 (m, 1H), 2.25-2.10 (m, 1H), 2.04-1.95 (m, 1H), 1.83 (m 1H), 1.65 (s, 3H), 1.63-1.57 (m, 1H), 1.49 (s, 18H), 1.46 (d, J=6.3 Hz, 3H), 1.08 (dd, J=16.0, 7.8 Hz, 1H); 13C NMR (101 MHz, CDCl3) δ 170.75, 157.45, 152.86, 142.27, 129.49, 121.17, 116.55, 112.39, 83.08, 83.01, 82.73, 77.41, 72.73, 57.27, 30.44, 28.80, 27.98, 19.74, 19.18, 18.23; HRMS-ESI (m/z) [M+Na]+ calcd for C29H43NNaO8, 556.2881; found, 556.2875.
Example 12B, Step 2
Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-7-isobutoxy-9-methyl-2-oxo-8-phenoxy-oxonan-3-yl]carbamate (C17)




A suspension of Pd/C (5% w/w Pd; 199 mg) and tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-7-(2-methylallyloxy)-2-oxo-8-phenoxy-oxonan-3-yl]carbamate (1.00 g, 1.87 mmol) in EtOAc (9.4 mL) was stirred rapidly at room temperature under one atmosphere (atm) of H2 overnight. The suspension was filtered through Celite®, washed with EtOAc (3×30 mL), and the combined extracts were concentrated to yield the title compound as a clear oil (980 mg, 98%): 1H NMR (400 MHz, CDCl3) δ 7.27-7.16 (m, 2H), 7.12-7.01 (m, 2H), 6.99-6.86 (m, 1H), 4.94-4.73 (m, 2H), 4.38 (dd, J=9.6, 7.3 Hz, 1H), 3.53 (ddd, J=7.1, 5.2, 1.7 Hz, 1H), 3.24 (dd, J=8.8, 6.6 Hz, 1H), 3.05 (dd, J=8.8, 6.3 Hz, 1H), 2.53-2.29 (m, 1H), 2.29-2.11 (m, 1H), 2.04 (s, 1H), 1.88-1.60 (m, 3H), 1.60-1.40 (m, 18H), 1.33 (d, J=6.4 Hz, 3H), 1.05 (dd, J=16.0, 7.8 Hz, 1H), 0.78 (d, J=6.7 Hz, 3H), 0.73 (d, J=6.7 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 170.84, 159.72, 152.86, 129.27, 121.17, 116.42, 83.13, 82.72, 82.70, 76.40, 72.72, 57.41, 30.58, 28.70, 28.49, 27.98, 19.36, 19.24, 19.21, 18.20; HRMS-ESI (m/z) [M+Na]+ calcd for C29H45NNaO8, 558.3037; found, 558.3030.
The following compounds were prepared and isolated using the methodology described in Example 12B, Step 2:
tert-Butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-isobutoxy-9-methyl-2-oxo-7-phenoxy-oxonan-3-yl]carbamate (C18)




Isolated as a white solid (430 mg; 100%): 1H NMR (400 MHz, CDCl3) δ 7.32-7.22 (m, 2H), 6.99-6.86 (m, 3H), 4.86 (dd, J=10.2, 8.2 Hz, 1H), 4.75 (dq, J=9.7, 6.3 Hz, 1H), 4.43-4.26 (m, 1H), 3.66-3.50 (m, 2H), 3.36 (dd, J=8.7, 6.7 Hz, 1H), 2.44-2.24 (m, 1H), 2.24-2.08 (m, 1H), 2.04-1.91 (m, 1H), 1.89-1.56 (m, 3H), 1.53-1.46 (m, 18H), 1.44 (d, J=6.3 Hz, 3H), 1.06 (dd, J=16.0, 7.9 Hz, 1H), 0.82 (d, J=6.7 Hz, 3H), 0.78 (d, J=6.7 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 170.78, 157.65, 152.86, 129.44, 121.06, 116.54, 83.33, 83.06, 82.71, 80.56, 72.93, 57.27, 30.46, 28.97, 28.85, 27.97, 19.39, 19.28, 19.17, 18.15; HRMS-ESI (m/z) [M+Na]+ calcd for C29H45NNaO8, 558.3037; found, 558.2994.
Example 12B, Step 3
Preparation of [(3S,7S,8S,9S)-7-isobutoxy-9-methyl-2-oxo-8-phenoxy-oxonan-3-yl]ammonium chloride (F3)




Prepared according to the methods described in Example 12A.
The following compounds were prepared and isolated using the methodology described in Example 12B, Step 3:
[(3S,7S,8S,9S)-8-Isobutoxy-9-methyl-2-oxo-7-phenoxy-oxonan-3-yl]ammonium chloride (F4)




Example 12C, Step 1
Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-(4-fluorophenoxy)-7-(4-methoxyphenoxy)-9-methyl-2-oxo-oxonan-3-yl]carbamate (C19)




To a stirred solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-8-(4-fluorophenoxy)-7-hydroxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (150 mg, 0.30 mmol) in toluene (1.51 mL) under N2 was added tri(p-methoxyphenyl)bismuth diacetate (391 mg, 0.603 mmol) followed by diacetoxycopper (10.9 mg, 0.060 mmol) and N-cyclohexyl-N-methylcyclohexanamine (129 microliters (μL), 0.603 mmol). The reaction mixture was heated for 18 h at 43° C. The reaction was concentrated and purified by column chromatography (0→100% EtOAc/hex) to yield the title compound (75 mg, 41%) as a yellow oil: 1H NMR (400 MHz, CDCl3) δ 7.07-6.97 (m, 2H), 6.96-6.85 (m, 2H), 6.81-6.69 (m, 4H), 4.99-4.85 (m, 2H), 4.47 (dd, J=9.6, 7.4 Hz, 1H), 4.34 (dt, J=5.5, 3.5 Hz, 1H), 3.73 (s, 3H), 2.37 (q, J=10.7 Hz, 1H), 2.22 (ddt, J=15.4, 9.6, 5.2 Hz, 1H), 2.12-1.98 (m, 1H), 1.95-1.80 (m, 1H), 1.73 (dd, J=14.5, 7.2 Hz, 1H), 1.51 (s, 18H), 1.40 (d, J=6.4 Hz, 3H), 1.15 (dd, J=16.0, 7.7 Hz, 1H); 19F NMR (376 MHz, CDCl3) δ −122.84; HRMS-ESI (m/z) [M+Na]+ calcd for C32H42FNNaO9, 626.2736; found, 626.2739.
Example 12C, Step 2
Preparation of [(3S,7S,8S,9S)-8-(4-fluorophenoxy)-7-(4-methoxyphenoxy)-9-methyl-2-oxo-oxonan-3-yl]ammonium chloride (F5)




Prepared according to the methods described in Example 12A.
Example 13
Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7-hydroxy-9-methyl-8-(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamate (C20)




A solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7,8-dihydroxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (100 mg, 0.25 mmol), bis(2-methylallyl) carbonate (51 mg, 0.30 mmol), dppf (14 mg, 0.025 mmol) and Pd2(dba)3 (11.4 mg, 0.012 mmol) in degassed THF (1.24 mL) was heated to 60° C. for 1.5 h. The solution was cooled to room temperature and purified by column chromatography (SiO2; 0→5% EtOAc/hexanes) to yield the title compound (61 mg, 54%) as a white solid: 1H NMR (400 MHz, CDCl3) δ 5.03-4.97 (m, 1H), 4.90 (s, 1H), 4.82 (dd, J=10.4, 7.1 Hz, 1H), 4.74 (dq, J=9.5, 6.3 Hz, 1H), 4.09 (s, 2H), 3.64-3.56 (m, 1H), 3.23 (dd, J=9.4, 7.7 Hz, 1H), 2.53 (d, J=1.5 Hz, 1H), 2.43-2.30 (m, 1H), 2.12-2.00 (m, 1H), 1.92-1.80 (m, 1H), 1.77 (m, 5H), 1.61-1.45 (m, 19H), 1.42 (d, J=6.4 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 170.73, 152.84, 141.85, 112.38, 85.49, 82.70, 77.62, 73.37, 72.70, 57.77, 34.76, 30.87, 27.96, 19.99, 19.67, 18.23; HRMS-ESI (m/z) [M+Na]+ calcd for C23H39NNaO8, 480.2568; found, 480.2572.
The following compounds were prepared and isolated using the appropriately substituted allyl carbonate and the methodology described in Example 13:
tert-Butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-hydroxy-9-methyl-7-(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamate (C21)




Isolated as a white solid (25 mg; 22%): 1H NMR (400 MHz, CDCl3) δ 5.01-4.95 (m, 1H), 4.91 (s, 1H), 4.85 (dd, J=9.5, 7.6 Hz, 1H), 4.80-4.67 (m, 1H), 4.01 (d, J=12.2 Hz, 1H), 3.83 (d, J=12.2 Hz, 1H), 3.56 (ddd, J=9.5, 7.7, 2.0 Hz, 1H), 3.21 (td, J=7.6, 2.1 Hz, 1H), 2.85 (d, J=2.0 Hz, 1H), 2.40-2.23 (m, 1H), 2.13-2.00 (m, 1H), 1.93 (dt, J=14.0, 6.9 Hz, 1H), 1.84-1.73 (m, 4H), 1.70-1.56 (m, 1H), 1.51 (s, 18H), 1.46-1.38 (m, 4H); 13C NMR (101 MHz, CDCl3) δ 170.74, 152.92, 141.77, 112.89, 82.69, 81.96, 75.76, 73.49, 73.25, 57.61, 31.12, 31.04, 27.98, 20.37, 19.67, 18.16; HRMS-ESI (m/z) [M+Na]+ calcd for C23H39NNaO8, 480.2568; found, 480.2576.
tert-Butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-7,8-bis(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamate (C22)




Isolated as a white solid (200 mg; 5%): 1H NMR (400 MHz, CDCl3) δ 5.03-4.91 (m, 2H), 4.90-4.75 (m, 3H), 4.67 (dq, J=9.0, 6.3 Hz, 1H), 4.25 (d, J=11.7 Hz, 1H), 3.99 (dd, J=21.0, 11.9 Hz, 2H), 3.90-3.79 (m, 1H), 3.56-3.35 (m, 2H), 2.44-2.27 (m, 1H), 2.12 (ddd, J=23.7, 9.0, 5.0 Hz, 1H), 2.02 (dt, J=13.3, 6.5 Hz, 1H), 1.74 (s, 3H), 1.75 (s, 3H), 1.72-1.54 (m, 3H), 1.51 (s, 18H), 1.40 (d, J=6.3 Hz, 3H), 1.03-0.91 (m, 1H); 13C NMR (101 MHz, CDCl3) δ 170.86, 152.90, 142.54, 142.48, 112.09, 111.94, 83.62, 82.67, 73.10, 72.99, 57.43, 30.55, 28.52, 27.98, 19.80, 19.70, 19.24, 18.12; EIMS m/z 534.8 ([M+Na]+)
tert-Butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-8-cyclopent-2-en-1-yloxy-7-hydroxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (C23)




Isolated as a yellow foam (344 mg, 41%): IR (neat) 3520, 2978, 2928, 1744, 1704, 1358 cm−1; 1H NMR (400 MHz, CDCl3) δ 6.09-6.04 (m, 1H), 5.96 (dq, J=5.9, 2.1 Hz, 0.5H), 5.86 (dq, J=5.8, 2.2 Hz, 0.5H), 4.88-4.63 (m, 3H), 3.55-3.39 (m, 1H), 3.34-3.28 (m, 1H), 2.61-1.99 (m, 7H), 1.92-1.69 (m, 4H), 1.51 (s, 18H), 1.44 (d, J=6.4 Hz, 1.5H), 1.42 (d, J=6.4 Hz, 1.5H); ESIMS m/z 492.3 ([M+Na]+).
Example 13A, Step 1
Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-7,8-diisobutoxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (C24)




To a solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-7,8-bis(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamate (333 mg, 0.651 mmol) in EtOAc (6.51 mL) was added Pd/C (10% w/w Pd, 34.6 mg, 0.033 mmol). The atmosphere was replaced with 1 atm hydrogen (balloon) and the reaction was stirred overnight at room temperature. The reaction mixture was filtered through Celite® and the pad was flushed with EtOAc. The filtrate was concentrated to provide the title compound (313 mg, 93%) as a white, crystalline solid: IR (thin film) 2957, 1742, 1724, 1470, 1366, 1347, 1245, 1104 cm−1; 1H NMR (400 MHz, CDCl3) δ 4.80 (dd, J=10.5, 8.0 Hz, 1H), 4.69-4.54 (m, 1H), 3.60 (dd, J=8.6, 6.2 Hz, 1H), 3.40-3.21 (m, 4H), 3.11 (dd, J=8.7, 6.3 Hz, 1H), 2.42-2.25 (m, 1H), 2.20-2.05 (m, 1H), 2.01 (m, 1H), 1.81 (tt, J=12.7, 6.3 Hz, 2H), 1.73-1.55 (m, 3H), 1.51 (s, 18H), 1.42-1.32 (m, 3H), 1.01-0.80 (m, 12H); 13C NMR (101 MHz, CDCl3) δ 170.91, 152.89, 84.27, 83.65, 82.64, 80.41, 75.84, 73.15, 57.46, 30.53, 29.07, 28.89, 28.20, 27.98, 19.58, 19.54, 19.39, 19.18, 18.12.
Example 13A, Step 2
Preparation of [(3S,7S,8S,9S)-7,8-diisobutoxy-9-methyl-2-oxo-oxonan-3-yl]ammonium chloride (F6)




Prepared according to the methods described in Example 12A.
Example 13B, Step 1
Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-hydroxy-7-isobutoxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (C25)




To a solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-hydroxy-9-methyl-7-(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamate (1.00 g, 2.19 mmol) in EtOAc (4 mL) in a vial was added Pd/C (5% w/w Pd, 0.233 g). The vial was evacuated and backfilled with hydrogen (1 atm), then stirred vigorously at room temperature. After stirring overnight, the reaction mixture was filtered through a pad of Celite® and concentrated to yield a white solid (1.06 g, 95%): IR (thin film) 3448, 3224, 2960, 2934, 2877, 1752, 1742, 1723, 1139, 1119 cm−1; 1H NMR (400 MHz, CDCl3) δ 4.85 (dd, J=9.4, 7.4 Hz, 1H), 4.73 (dq, J=9.5, 6.3 Hz, 1H), 3.51 (ddd, J=9.5, 7.6, 1.8 Hz, 1H), 3.35 (dd, J=8.9, 6.7 Hz, 1H), 3.11 (dd, J=8.8, 6.3 Hz, 2H), 2.93 (d, J=1.8 Hz, 1H), 2.30 (dtd, J=14.0, 9.8, 1.9 Hz, 1H), 2.13-2.00 (m, 1H), 1.95-1.74 (m, 3H), 1.68-1.61 (m, 1H), 1.61-1.58 (m, 1H), 1.51 (s, 18H), 1.42 (d, J=6.3 Hz, 3H), 0.91 (dd, J=6.7, 1.2 Hz, 6H); 13C NMR (101 MHz, CDCl3) δ 170.77, 152.92, 82.71, 82.40, 76.26, 75.85, 73.63, 57.69, 31.43, 31.22, 28.69, 27.99, 20.52, 19.41, 19.36, 18.19; HRMS-ESI (m/z) [M+Na]+ calcd for C23H41NNaO8, 482.2724; found, 482.2718.
The following compounds were prepared and isolated using the methodology described in Example 13B, Step 1:
tert-Butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7-hydroxy-8-isobutoxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (C26)




Isolated as a colorless oil (600 mg, 100%): 1H NMR (400 MHz, CDCl3) δ 4.81 (dd, J=10.5, 6.9 Hz, 1H), 4.77-4.66 (m, 1H), 3.60-3.50 (m, 1H), 3.47 (dd, J=8.6, 6.3 Hz, 1H), 3.40 (dd, J=8.6, 6.7 Hz, 1H), 3.12 (dd, J=9.5, 7.7 Hz, 1H), 2.63-2.56 (m, 1H), 2.36 (ddt, J=13.7, 11.1, 4.9 Hz, 1H), 2.12-1.98 (m, 1H), 1.95-1.75 (m, 4H), 1.53-1.50 (m, 1H), 1.51 (s, 18H), 1.41 (d, J=6.3 Hz, 3H), 0.93 (dd, J=6.7, 3.3 Hz, 6H); 13C NMR (101 MHz, CDCl3) δ 170.72, 152.82, 85.27, 82.67, 80.81, 72.95, 72.82, 57.87, 35.34, 30.89, 29.03, 27.95, 20.13, 19.33, 19.23, 18.26.
Example 13B, Step 2
Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-7-isobutoxy-8-(4-methoxyphenoxy)-9-methyl-2-oxo-oxonan-3-yl]carbamate (C27)




A vial was charged with tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-hydroxy-7-isobutoxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (50 mg, 0.11 mmol), tris(p-methoxyphenyl)bismuth diacetate (106 mg, 0.163 mmol), toluene (544 μl) and diacetoxycopper (2.0 mg, 11 μmol). N-cyclohexyl-N-methylcyclohexanamine (46.2 μl, 0.218 mmol) was added and the reaction was heated to 50° C. and stirred overnight. The heterogeneous mixture was filtered through a plug of Celite®, the filtrate concentrated, and the residue purified by automated flash chromatography (0→50% EtOAc/hexanes) to afford a colorless semi-solid (43 mg, 69%): 1H NMR (400 MHz, CDCl3) δ 7.01 (d, J=9.1 Hz, 2H), 6.79 (d, J=9.1 Hz, 2H), 4.96-4.72 (m, 2H), 4.23 (dd, J=9.6, 7.3 Hz, 1H), 3.76 (s, 3H), 3.51 (ddd, J=7.1, 5.1, 1.8 Hz, 1H), 3.24 (dd, J=8.8, 6.7 Hz, 1H), 3.08 (dd, J=8.8, 6.2 Hz, 1H), 2.44-2.33 (m, 1H), 2.18 (dddd, J=15.5, 10.0, 8.1, 5.1 Hz, 1H), 2.05 (dddd, J=13.6, 8.2, 6.3, 1.7 Hz, 1H), 1.83-1.64 (m, 3H), 1.52 (s, 18H), 1.34 (d, J=6.3 Hz, 3H), 1.03 (ddt, J=15.8, 7.6, 1.9 Hz, 1H), 0.79 (dd, J=18.5, 6.7 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 170.85, 154.09, 154.02, 152.86, 117.55, 114.37, 83.88, 83.14, 82.73, 76.36, 72.80, 57.40, 55.68, 30.57, 28.73, 28.38, 27.98, 19.43, 19.29, 19.21, 18.28; IR (thin film) 2977, 1744, 1704, 1506, 1140 cm−1; HRMS-ESI (m/z) [M+Na]+ calcd for C30H47NNaO9, 588.3143; found, 588.3146.
Example 13B, Step 3
Preparation of [(3S,7S,8S,9S)-7-isobutoxy-8-(4-methoxyphenoxy)-9-methyl-2-oxo-oxonan-3-yl]ammonium chloride (F7)




Prepared according to the methods described in Example 12A.
Example 13C, Step 1
Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-8-(2-methylallyloxy)-2-oxo-7-phenoxy-oxonan-3-yl]carbamate (An alternate method to prepare C16)




A solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7-hydroxy-9-methyl-8-(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamate (56.0 mg, 0.122 mmol), triphenylbismuth diacetate (137 mg, 0.245 mmol) and diacetoxycopper (4.4 mg, 0.024 mmol) in toluene (1224 μl) was stirred at 40° C. overnight. The reaction mixture was filtered thru Celite®, the pad washed with toluene (2×10 mL), and the filtrate concentrated to yield a light blue foam. Purification by column chromatography (SiO2; 0→20% EtOAc/hexanes) afforded the title compound (45 mg, 69%) as a white solid: See Compound 16 (Example 12B, Step 1) for analytical data.
Example 13C, Step 2
Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-isobutoxy-9-methyl-2-oxo-7-phenoxy-oxonan-3-yl]carbamate (An alternate method to prepare C18)




Prepared according to the procedure described for example 12B step 2 and isolated as a clear oil (430 mg; 100%): 1H NMR (400 MHz, CDCl3) δ 7.32-7.22 (m, 2H), 6.99-6.86 (m, 3H), 4.86 (dd, J=10.2, 8.2 Hz, 1H), 4.75 (dq, J=9.7, 6.3 Hz, 1H), 4.43-4.26 (m, 1H), 3.66-3.50 (m, 2H), 3.36 (dd, J=8.7, 6.7 Hz, 1H), 2.44-2.24 (m, 1H), 2.24-2.08 (m, 1H), 2.04-1.91 (m, 1H), 1.89-1.56 (m, 3H), 1.53-1.46 (m, 18H), 1.44 (d, J=6.3 Hz, 3H), 1.06 (dd, J=16.0, 7.9 Hz, 1H), 0.82 (d, J=6.7 Hz, 3H), 0.78 (d, J=6.7 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 170.78, 157.65, 152.86, 129.44, 121.06, 116.54, 83.33, 83.06, 82.71, 80.56, 72.93, 57.27, 30.46, 28.97, 28.85, 27.97, 19.39, 19.28, 19.17, 18.15; HRMS-ESI (m/z) [M+Na]+ calcd for C29H45NNaO8, 558.3037; found, 558.2994.
Example 13C, Step 3
Preparation of [(3S,7S,8S,9S)-8-isobutoxy-9-methyl-2-oxo-7-phenoxy-oxonan-3-yl]ammonium chloride (An alternative route to prepare F4)




Prepared according to the methods described in Example 12B, Step 3.
Example 13D, Step 1
Preparation of [(2S,3S,4S,8S)-8-[bis(tert-butoxycarbonyl)amino]-3-isobutoxy-2-methyl-9-oxo-oxonan-4-yl]cyclopentanecarboxylate (C28)




To a 10 mL screw-cap vial were added tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7-hydroxy-8-isobutoxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (200 mg, 0.44 mmol), pyridine (105 μl, 1.31 mmol) and CH2Cl2 (2176 μl), followed by cyclopentanecarbonyl chloride (79 μl, 0.65 mmol). The vial was sealed under N2 and the reaction was magnetically stirred overnight. The crude mixture was purified by column chromatography (SiO2, 1→25% acetone/hexanes) to yield the title compound (203 mg, 84%): 1H NMR (400 MHz, CDCl3) δ 4.92 (ddd, J=7.4, 5.3, 1.9 Hz, 1H), 4.85 (dd, J=10.3, 8.0 Hz, 1H), 4.72 (dq, J=9.7, 6.3 Hz, 1H), 3.45 (dd, J=9.6, 7.6 Hz, 1H), 3.39-3.28 (m, 2H), 2.72 (p, J=7.9 Hz, 1H), 2.40-2.26 (m, 1H), 2.17-1.95 (m, 2H), 1.92-1.69 (m, 8H), 1.58 (ddd, J=10.7, 5.5, 3.0 Hz, 3H), 1.51 (s, 18H), 1.41 (d, J=6.3 Hz, 3H), 1.12-1.00 (m, 1H), 0.86 (t, J=7.0 Hz, 6H); 13C NMR (101 MHz, CDCl3) δ 175.65, 170.57, 152.78, 82.78, 82.17, 80.05, 77.85, 72.95, 57.22, 44.14, 30.53, 30.22, 29.75, 29.58, 28.99, 27.97, 25.79, 19.36, 19.28, 18.04; ESIMS m/z 578.4 [(M+Na)+].
The following compounds were prepared and isolated using the methodology described in Example 13D, Step 1:
[(2S,3S,4S,8S)-8-[bis(tert-butoxycarbonyl)amino]-4-isobutoxy-2-methyl-9-oxo-oxonan-3-yl]cyclopentanecarboxylate (C29)




Isolated as a white solid (98%): mp 101-106° C.; 1H NMR (400 MHz, CDCl3) δ 5.12 (dd, J=9.7, 7.8 Hz, 1H), 4.88-4.73 (m, 2H), 3.36 (ddd, J=7.5, 5.2, 2.0 Hz, 1H), 3.26 (dd, J=8.7, 6.3 Hz, 1H), 2.97 (dd, J=8.7, 6.6 Hz, 1H), 2.72 (p, J=7.9 Hz, 1H), 2.36 (tdd, J=12.5, 10.3, 1.9 Hz, 1H), 2.22-1.98 (m, 2H), 1.95-1.55 (m, 10H), 1.51 (s, 18H), 1.26 (d, J=6.4 Hz, 3H), 1.02 (ddt, J=15.7, 7.3, 2.0 Hz, 1H), 0.84 (d, J=6.7 Hz, 6H); 13C NMR (101 MHz, CDCl3) δ 175.60, 170.93, 152.83, 82.71, 81.23, 76.10, 75.21, 71.65, 57.37, 43.98, 30.58, 30.13, 29.74, 28.69, 28.36, 27.97, 25.81, 25.70, 19.38, 19.34, 18.96, 17.38; ESIMS m/z 578.5 ([M+Na]+).
Example 13D, Step 2
Preparation of [(3S,7S,8S,9S)-7-(cyclopentanecarbonyloxy)-8-isobutoxy-9-methyl-2-oxo-oxonan-3-yl]ammonium chloride (F8)




Prepared according to the methods described in Example 12A.
The following compounds were prepared and isolated using the methodology described in Example 13D, Step 2:
[(3S,7S,8S,9S)-8-(cyclopentanecarbonyloxy)-7-isobutoxy-9-methyl-2-oxo-oxonan-3-yl]ammonium chloride (F9)




Example 13E, Step 1
Preparation of (2S,3S,4S,8S)-8-((bis tert-butoxycarbonyl)amino)-2-methyl-4-((2-methylallyl)oxy)-9-oxooxonan-3-yl cyclopropanecarboxylate (C30)




To a solution tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-hydroxy-9-methyl-7-(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamate (500 mg, 1.09 mmol) in CH2Cl2 (2.2 mL) was added pyridine (0.265 mL, 3.28 mmol) and cyclopropanecarbonyl chloride (0.149 mL, 1.64 mmol). The resulting solution was stirred at room temperature for 16 h, then purified by automated silica gel column chromatography (0→100% EtOAc/hexanes) to provide a light yellow solid (599 mg, 99%): IR (thin film) 2979, 2938, 1737, 1703, 1355, 1159 cm−; 1H NMR (400 MHz, CDCl3) δ 5.14 (dd, J=9.7, 7.8 Hz, 1H), 4.95-4.66 (m, 4H), 3.94 (d, J=12.3 Hz, 1H), 3.76 (d, J=12.2 Hz, 1H), 3.46 (ddd, J=7.6, 5.3, 1.9 Hz, 1H), 2.37 (q, J=11.9, 11.3 Hz, 1H), 2.21-2.00 (m, 2H), 1.87-1.74 (m, 1H) 1.71 (s, 3H), 1.51 (s, 18H), 1.28 (d, J=6.3 Hz, 3H), 1.17 (dt, J=6.9, 4.2 Hz, 1H), 1.11-0.97 (m, 4H), 0.87 (dq, J=6.4, 3.7 Hz, 2H); 13C NMR (101 MHz, CDCl3) δ 173.98, 170.89, 152.84, 142.11, 112.39, 82.73, 80.01, 75.46, 73.07, 71.66, 57.36, 30.57, 28.55, 27.97, 19.41, 19.03, 17.36, 12.89, 10.18, 8.49, 8.43.
Example 13E, Step 2
Preparation of (2S,3S,4S,8S)-8-((bis tert-butoxycarbonyl)amino)-4-isobutoxy-2-methyl-9-oxooxonan-3-yl cyclopropanecarboxylate (C31)




Prepared according to the methodology described in Example 13B, Step 1 to give the title compound (424 mg, 89%) as a white solid: IR (thin film) 2978, 1739, 1706, 1162 cm−1; 1H NMR (400 MHz, CDCl3) δ 5.11 (dd, J=9.7, 7.8 Hz, 1H), 4.88-4.70 (m, 2H), 3.36 (ddd, J=7.6, 5.2, 2.0 Hz, 1H), 3.30 (dd, J=8.8, 6.1 Hz, 1H), 2.98 (dd, J=8.8, 6.8 Hz, 1H), 2.36 (dddd, J=13.9, 12.1, 10.1, 1.8 Hz, 1H), 2.22-1.97 (m, 2H), 1.85-1.69 (m, 2H), 1.70-1.55 (m, 2H), 1.51 (s, 18H), 1.27 (d, J=6.4 Hz, 3H), 1.12-0.96 (m, 3H), 0.91-0.82 (m, 8H); 13C NMR (101 MHz, CDCl3) δ 173.94, 170.92, 152.84, 82.72, 81.25, 76.30, 75.50, 71.65, 57.37, 30.61, 28.63, 27.97, 19.32, 19.27, 19.00, 17.35, 12.89, 8.43, 8.36; HRMS-ESI (m/z) [M+H]+ calcd for C2H46NO9, 528.3167; found, 528.3167.
Example 13E, Step 3
Preparation of [(3S,7S,8S,9S)-8-(cyclopropanecarbonyloxy)-7-isobutoxy-9-methyl-2-oxo-oxonan-3-yl]ammonium chloride (F10)




Prepared according to the methods described in Example 12A.
Example 13F, Step 1
Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-7-(2-methylallyloxy)-2-oxo-8-[(E)-4,4,4-trifluorobut-2-enoxy]oxonan-3-yl]carbamate (C32)




A solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-hydroxy-9-methyl-7-(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamate (499 mg, 1.09 mmol), (E)-bis tert-butyl (4,4,4-trifluorobut-2-en-1-yl) carbonate (493 mg, 2.18 mmol), dppf (60.5 mg, 0.109 mmol) and Pd2(dba)3 (49.9 mg, 0.055 mmol) in degassed THF (5453 μl) was heated to 60° C. for 1.5 h. The solution was cooled to room temperature and purified by automated flash chromatography (SiO2; 0→10% EtOAc/hexanes) to yield the title compound as a yellow semi-solid (292 mg, 73%): 1H NMR (400 MHz, CDCl3) δ 6.44-6.36 (m, 1H), 5.96-5.78 (m, 1H), 4.96-4.92 (m, 1H), 4.88-4.85 (m, 1H), 4.82 (dd, J=10.3, 8.0 Hz, 1H), 4.73-4.64 (m, 1H), 4.46 (m, 1H), 4.30-4.21 (m, 1H), 3.96 (d, J=12.1 Hz, 1H), 3.79 (d, J=12.1 Hz, 1H), 3.50-3.39 (m, 2H), 2.36 (dd, J=12.0, 2.6 Hz, 1H), 2.19-1.98 (m, 2H), 1.72 (s, 3H), 1.70-1.59 (m, 2H), 1.51 (s, 18H), 1.38 (d, J=6.3 Hz, 3H), 0.97 (dd, J=16.3, 7.7 Hz, 1H); 13C NMR (101 MHz, CDCl3) δ 170.79, 152.89, 142.25, 136.73, 118.34, 118.01, 112.25, 84.21, 83.30, 82.74, 77.21, 72.89, 72.49, 71.03, 57.31, 30.50, 28.23, 27.98, 19.59, 19.18, 18.04; ESIMS m/z 588.3 ([M+Na]+).
Example 13F, Step 2
Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-7-isobutoxy-9-methyl-2-oxo-8-(4,4,4-trifluorobutoxy)oxonan-3-yl]carbamate (C33)




The tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-7-(2-methylallyloxy)-2-oxo-8-[(E)-4,4,4-trifluorobut-2-enoxy]oxonan-3-yl]carbamate (451 mg, 0.80 mmol) was dissolved in EtOAc (4 mL) in a vial and Pd/C (5% w/w Pd, 85 mg, 0.040 mmol) was added. The vial was evacuated and backfilled with hydrogen (1 atm), then stirred vigorously at room temperature. After stirring for 16 h, the reaction mixture was filtered through a pad of Celite® and concentrated to provide a white solid (454 mg, 100%) 1H NMR (400 MHz, CDCl3) δ 4.80 (dd, J=10.4, 8.0 Hz, 1H), 4.62 (pd, J=6.2, 2.0 Hz, 1H), 3.83 (dt, J=9.3, 6.0 Hz, 1H), 3.64 (dt, J=9.3, 6.1 Hz, 1H), 3.40-3.20 (m, 3H), 3.08 (dd, J=8.7, 6.2 Hz, 1H), 2.45-2.28 (m, 1H), 2.25-2.04 (m, 2H), 2.07-1.95 (m, 1H), 1.88-1.73 (m, 3H), 1.73-1.57 (m, 3H), 1.51 (s, 18H), 1.36 (d, J=6.4 Hz, 3H), 0.95-0.83 (m, 7H); 19F NMR (376 MHz, CDCl3) δ −66.43; 13C NMR (101 MHz, CDCl3) δ 170.88, 152.89, 84.07, 83.91, 82.70, 75.65, 72.75, 71.58, 57.39, 31.05, 30.76, 30.50, 28.88, 27.97, 23.07, 23.05, 19.55, 19.47, 19.11, 18.09; ESIMS m/z 592.3 ([M+Na]+).
Example 13F, Step 3
Preparation of [(3S,7S,8S,9S)-7-isobutoxy-9-methyl-2-oxo-8-(4,4,4-trifluorobutoxy)oxonan-3-yl]ammonium chloride (F11)




Prepared according to the methods described in Example 12A.
Example 13G, Step 1
Preparation of tert-butyl N-[(3S,7S,8S,9S)-7-allyloxy-8-cyclopent-2-en-1-yloxy-9-methyl-2-oxo-oxonan-3-yl]-N-tert-butoxycarbonyl-carbamate (C34)




To a solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-8-cyclopent-2-en-1-yloxy-7-hydroxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (200 mg, 0.43 mmol), Pd2(dba)3 (39.0 mg, 0.043 mmol) and dppf (47.2 mg, 0.085 mmol) in THF (2.1 mL) at room temperature was added allyl tert-butyl carbonate (202 mg, 1.28 mmol). The reaction was stirred at 60° C. overnight. The reaction mixture was concentrated and purified by column chromatography on SiO2 (5→25% EtOAc/hexanes) to yield the title compound as a yellow oil (160 mg, 74%): IR (thin film) 2978, 2933, 1742, 1703; 1H NMR (400 MHz, CDCl3) δ 6.05-5.84 (m, 3H), 5.30-5.24 (m, 1H), 5.17-5.13 (m, 1H), 4.93-4.76 (m, 2H), 4.68-4.53 (m, 1H), 4.13-4.05 (m, 1H), 3.98-3.92 (m, 1H), 3.54-3.50 (m, 1H), 3.45-3.38 (m, 1H), 2.52-2.29 (m, 2H), 2.28-1.89 (m, 4H), 1.81-1.57 (m, 3H), 1.51 (s, 18H), 1.39 (d, J=6.4 Hz, 3H), 1.00-0.88 (m, 1H); ESIMS m/z 532.4 ([M+Na]+).
Example 13G, Step 2
Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-(cyclopentoxy)-9-methyl-2-oxo-7-propoxy-oxonan-3-yl]carbamate (C35)




Prepared according to the methodology described in Example 13F, Step 2 to give the title compound (286 mg, 95%) as a colorless oil): 1H NMR (400 MHz, CDCl3) δ 4.79 (dd, J=10.6, 7.9 Hz, 1H), 4.57 (dq, J=9.5, 6.4 Hz, 1H), 4.32-4.25 (m, 1H), 3.53-3.37 (m, 2H), 3.35-3.27 (m, 2H), 2.42-2.28 (m, 1H), 2.19-1.95 (m, 2H), 1.83-1.53 (m, 12H), 1.51 (s, 18H), 1.37 (d, J=6.4 Hz, 3H), 0.92 (t, J=7.4 Hz, 3H), 0.90-0.87 (m, 1H); 13C NMR (101 MHz, CDCl3) δ 170.93, 152.86, 84.28, 83.25, 82.60, 81.26, 73.34, 70.89, 57.47, 32.91, 32.35, 30.50, 28.36, 27.94, 23.33, 23.23, 23.19, 19.20, 18.20, 10.76; ESIMS m/z 536.5 ([M+Na]+).
Example 13G, Step 3
Preparation of [(3S,7S,8S,9S)-8-(cyclopentoxy)-9-methyl-2-oxo-7-propoxy-oxonan-3-yl]ammonium chloride (F11)




Prepared according to the methods described in Example 12A.
Example 14
Preparation of (2S,3S,4S,8S)-8-((bis tert-butoxycarbonyl)amino)-2-methyl-9-oxooxonane-3,4-diyl dicyclopentanecarboxylate (C36)




A 20 mL vial was charged with tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7,8-dihydroxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (300 mg, 0.74 mmol), CH2Cl2 (3.7 mL), and DMAP (182 mg, 1.49 mmol). Cyclopentanecarbonyl chloride (181 μL, 1.49 mmol) was added dropwise to the colorless solution, which then became dark brown. The reaction flask was placed in a room temperature water bath. The reaction mixture was stirred overnight, concentrated, and partially purified using automated flash chromatography (SiO2; 0→100% EtOAc/hexanes) to give fractions that all contained an impurity derived from the cyclopentanecarbonyl chloride. The impure fractions were combined, washed with 1N HCl, then saturated NaHCO3 and brine, and then concentrated to give a colorless oil (80.2 mg, 18%): IR (thin film) 2954, 1741, 1706, 1140 cm−1; 1H NMR (400 MHz, CDCl3) δ 5.24 (dd, J=9.9, 8.1 Hz, 1H), 5.00 (ddd, J=7.8, 5.2, 2.2 Hz, 1H), 4.92-4.81 (m, 2H), 2.83-2.72 (m, 2H), 2.36 (dddd, J=13.8, 12.1, 10.1, 1.8 Hz, 1H), 2.19-2.00 (m, 2H), 1.98-1.78 (m, 5H), 1.78-1.54 (m, 13H), 1.51 (s, 18H), 1.28 (d, J=6.3 Hz, 3H), 1.19 (ddt, J=16.2, 7.8, 2.2 Hz, 1H); 13C NMR (101 MHz, CDCl3) δ 175.75, 175.55, 170.61, 152.75, 99.98, 82.86, 74.97, 73.67, 71.33, 57.12, 43.91, 43.80, 30.46, 30.07, 29.98, 29.93, 29.79, 29.62, 27.96, 25.76, 25.69, 19.08, 17.35; HRMS-ESI (m/z) [M+Na]+ calcd for C31H49NNaO10, 618.3249; found, 618.3250.
Example 14A
Preparation of [(3S,7S,8S,9S)-7,8-bis(cyclopentanecarbonyloxy)-9-methyl-2-oxo-oxonan-3-yl]ammonium chloride (F12)




Prepared according to the methods described in Example 12A.
Example 15, Step 1
Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-7-(2-methylallyloxy)-2-oxo-8-[3-oxobut-1-enoxy]oxonan-3-yl]carbamate (C37)




To a 100 mL round bottomed flask were charged tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-hydroxy-9-methyl-7-(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamate (800 mg, 1.75 mmol), DABCO (9.8 mg, 0.087 mmol) and CH2Cl2 (8742 μl). The colorless solution was cooled to 0° C., then but-3-yn-2-one (163 μl, 2.10 mmol) was added dropwise over 10 min. The solution became dark brown. After stirring for 2 h, the reaction mixture was concentrated and purified by automated flash chromatography (SiO2; 0→100% EtOAc/hexanes) to afford a white solid as an approximate 4:1 mixture of E/Z isomers (0.953 g, 100%): IR (thin film) 2976, 2937, 1742, 1727, 1632, 1139, 1119 cm−1; 1H NMR (Major isomer; 400 MHz, CDCl3) δ 7.50 (d, J=12.3 Hz, 1H), 5.67 (d, J=12.4 Hz, 1H), 4.95-4.76 (m, 4H), 3.94-3.86 (m, 2H), 3.76 (d, J=11.9 Hz, 1H), 3.46 (ddd, J=7.3, 4.9, 1.9 Hz, 1H), 2.49-2.32 (m, 1H), 2.21-2.11 (m, 1H), 2.16 (s, 3H), 2.10-2.01 (m, 1H), 1.75-1.64 (m, 5H), 1.52 (s, 18H), 1.35 (d, J=6.4 Hz, 3H), 1.07-0.96 (m, 1H); 13C NMR (101 MHz, CDCl3) δ 197.43, 170.60, 164.05, 152.85, 141.82, 112.84, 108.78, 87.97, 82.88, 81.36, 73.01, 71.03, 57.12, 30.41, 27.97, 27.80, 27.50, 19.59, 19.07, 17.96; HRMS-ESI (m/z) [M+Na]+ calcd for C27H43NNaO9, 548.2830; found, 548.2826.
Example 15, Step 2
Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-7-isobutoxy-9-methyl-2-oxo-8-(3-oxobutoxy)oxonan-3-yl]carbamate (C38)




A round bottomed flask was charged with tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-7-(2-methylallyloxy)-2-oxo-8-[3-oxobut-1-enoxy]oxonan-3-yl]carbamate (954 mg, 1.82 mmol), Pd/C (5% w/w Pd, 193 mg, 0.091 mmol), and EtOAc (9 mL). The flask was evacuated and backfilled with N2, then evacuated and backfilled with H2. The reaction mixture was stirred vigorously at room temperature overnight. The crude reaction mixture was filtered through a plug of Celite® and the filtrate concentrated to give a crude solid. The solid was purified by automated flash chromatography (SiO2; 0→100% EtOAc/hexanes) to give a white solid (785 mg, 82%): IR (thin film) 2977, 2937, 1743, 1704, 1356, 1141 cm−1; 1H NMR (400 MHz, CDCl3) δ 4.80 (dd, J=10.5, 8.0 Hz, 1H), 4.65-4.53 (m, 1H), 4.02 (dt, J=9.5, 6.0 Hz, 1H), 3.89 (ddd, J=9.5, 7.1, 5.7 Hz, 1H), 3.36-3.23 (m, 3H), 3.11 (dd, J=8.8, 6.2 Hz, 1H), 2.74-2.56 (m, 2H), 2.41-2.26 (m, 1H), 2.17 (s, 3H), 2.15-2.06 (m, 1H), 2.03-1.96 (m, 1H), 1.87-1.76 (m, 1H), 1.73-1.60 (m, 2H), 1.51 (d, J=2.4 Hz, 18H), 1.35 (d, J=6.3 Hz, 3H), 0.91 (dd, J=6.7, 1.4 Hz, 6H), 0.87 (dd, J=7.1, 1.9 Hz, 1H); 13C NMR (101 MHz, CDCl3) δ 207.19, 170.86, 152.87, 84.02, 83.99, 82.67, 75.65, 72.76, 68.23, 57.39, 44.20, 30.49, 28.89, 28.06, 27.97, 19.56, 19.49, 19.13, 18.02; HRMS-ESI (m/z) [M+Na]+ calcd for C27H47NNaO9, 552.3143; found, 552.3158.
Example 15, Step 3
Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-7-isobutoxy-8-(3-methoxybutoxy)-9-methyl-2-oxo-oxonan-3-yl]carbamate (C39)




The tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-7-isobutoxy-9-methyl-2-oxo-8-(3-oxobutoxy)oxonan-3-yl]carbamate (400 mg, 0.76 mmol) was dissolved in MeOH (3.8 mL) and cooled to 0° C. under N2, and NaBH4 (5 mg, 1.72 mmol) was added in one portion. The reaction was stirred for 2.5 h and then quenched by the addition of saturated aqueous NH4Cl solution. The mixture was extracted with EtOAc, and the extracts were washed with brine, dried over Na2SO4, filtered, and concentrated to afford tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-(3-hydroxybutoxy)-7-isobutoxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (382 mg, 95%) as a colorless oil, which was used without further purification. An oven-dried round bottom flask was charged with the diastereomeric mixture of the alcohol (405 mg, 0.762 mmol), Proton Sponge® (653 mg, 3.05 mmol), and CH2Cl2 (5 mL). Trimethyloxonium tetrafluoroborate (225 mg, 1.52 mmol) was added in one portion to the colorless solution. A white suspension formed, and the mixture was stirred at room temperature. After stirring for 6 h, the reaction was quenched by the addition of saturated aqueous NaHCO3 (3 mL) and the phases were separated. The aqueous layer was extracted with CH2Cl2 and the combined organic layers were washed with brine, passed through a phase separator cartridge, concentrated, and purified by automated flash chromatography (SiO2; 0→100% EtOAc/hexanes) to afford a light pink oil as a mixture of diastereomers (328 mg, 79%): IR (thin film) 2935, 1745, 1706, 1142 cm−1; 1H NMR (400 MHz, CDCl3) δ 4.91-4.75 (m, 1H), 4.71-4.51 (m, 1H), 4.02-3.93 (m, 1H), 3.91-3.78 (m, 1H), 3.74-3.59 (m, 1H), 3.50-3.36 (m, 1H), 3.36-3.31 (m, 2H), 3.30 (s, 2H), 3.29-3.22 (m, 1H), 3.13 (tt, J=8.7, 6.1 Hz, 1H), 2.43-2.27 (m, 1H), 2.18-1.92 (m, 2H), 1.90-1.75 (m, 1H), 1.75-1.59 (m, 4H), 1.51 (s, 18H), 1.43-1.33 (m, 3H), 1.18 (dd, J=6.2, 2.9 Hz, 1H), 1.14-1.12 (m, 2H), 0.96-0.85 (m, 7H); 13C NMR (101 MHz, CDCl3) δ 170.92, 170.90, 152.89, 85.49, 84.82, 84.27, 84.14, 83.71, 82.68, 82.66, 82.61, 76.35, 75.95, 75.91, 75.53, 73.48, 73.11, 72.87, 61.27, 58.72, 57.44, 57.40, 56.51, 36.20, 32.47, 30.57, 30.54, 29.01, 28.87, 28.84, 28.29, 28.24, 19.63, 19.54, 19.49, 19.37, 19.15, 18.02, 17.92, 17.72, 15.73, 13.96; HRMS-ESI (m/z) [M+Na]+ calcd for C28H51NNaO9, 568.3456; found, 568.3453.
Example 15, Step 4
Preparation of [(3S,7S,8S,9S)-8-(3-methoxybutoxy)-7-isobutoxy-9-methyl-2-oxo-oxonan-3-yl]ammonium chloride (F13)




Prepared using the methodology described in Example 12A.
Example 16A
Preparation of 3-hydroxy-4-methoxy-N-((3S,7S,8S,9S)-9-methyl-7,8-bis((2-methylallyl)oxy)-2-oxooxonan-3-yl)pyridine-2-carboxamide (F14)




To a suspension of the [(3S,7S,8S,9S)-9-methyl-7,8-bis(2-methylallyloxy)-2-oxo-oxonan-3-yl]ammonium chloride (256 mg, 0.736 mmol) and 3-hydroxy-4-methoxypicolinic acid (137 mg, 0.809 mmol) in CH2Cl2 (6.0 ml) was added Hünig's base (0.422 ml, 2.42 mmol) followed by PyBOP (421 mg, 0.809 mmol). The reaction was stirred at room temperature for 90 min. The solvent was then removed and the resulting crude residue was purified by automated silica gel column chromatography (1→66% acetone/hexanes) to afford the title compound (246 mg, 72%) as a white foam.
Example 16B
Preparation of N-[(3S,7S,8S,9S)-7,8-dibenzyloxy-9-methyl-2-oxo-oxonan-3-yl]-3-hydroxy-4-methoxypyridine-2-carboxamide (F15)




To a suspension of the [(3S,7S,8S,9S)-7,8-dibenzyloxy-9-methyl-2-oxo-oxonan-3-yl]ammonium chloride (220 mg, 0.52 mmol) and 3-hydroxy-4-methoxypicolinic acid (124 mg, 0.733 mmol) in CH2Cl2 (5.2 mL) was added N-methylmorpholine (0.346 mL, 3.14 mmol) followed by HATU (299 mg, 0.786 mmol). The mixture was stirred at room temperature for 5 h, then the solvent was removed and the crude residue was purified by automated silica gel column chromatography (5→20% acetone/hexanes) to afford the title compound (124 mg, 44.3%) as a hard white foam.
Example 17A
Preparation of [4-methoxy-2-[[(3S,7S,8S,9S)-9-methyl-7,8-bis(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamoyl]-3-pyridyl]oxymethyl acetate (F16)




To a screw-cap vial were added 3-hydroxy-4-methoxy-N-((3S,7S,8S,9S)-9-methyl-7,8-bis((2-methylallyl)oxy)-2-oxooxonan-3-yl)pyridine-2-carboxamide (110 mg, 0.24 mmol) and K2CO3 (65.7 mg, 0.476 mmol), followed by acetone (2.38 ml). Then, bromomethyl acetate (33 μL, 0.34 mmol) was added dropwise and the reaction was heated to 50° C. for 1 h. The reaction mixture was cooled to room temperature, filtered through a plug of glass wool, and then the solvent was removed. The crude residue was purified by automated silica gel column chromatography (1-50% acetone/hexanes) to afford the title compound (98.9 mg, 78%) as a colorless oil.
Example 17B
Preparation of [4-methoxy-2-[[(3S,7S,8S,9S)-9-methyl-7,8-bis(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamoyl]-3-pyridyl]oxymethyl-2-methylpropanoate (F17)




To a screw-cap vial were added 3-hydroxy-4-methoxy-N-((3S,7S,8S,9S)-9-methyl-7,8-bis((2-methylallyl)oxy)-2-oxooxonan-3-yl)pyridine-2-carboxamide (110 mg, 0.24 mmol), powdered Na2CO3 (50.4 mg, 0.476 mmol), and NaI (5.4 mg, 0.036 mmol) followed by acetone (2.38 ml). Then, chloromethyl isobutyrate (0.042 ml, 0.33 mmol) was added dropwise and the reaction was heated to 50° C. for 14 h. The reaction mixture was cooled to room temperature, filtered through a plug of glass wool, and then the solvent was evaporated. The crude residue was purified by automated silica gel column chromatography (1→50% acetone/hexanes) to afford the title compound (127.9 mg, 96%) as a colorless oil.
Example 17C
Preparation of [2-[[(3S,7S,8S,9S)-8-isobutoxy-9-methyl-7-(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamoyl]-4-methoxy-3-pyridyl]acetate (F18)




To a screw-cap vial were added 3-hydroxy-N-[(3S,7S,8S,9S)-8-isobutoxy-9-methyl-7-(2-methylallyloxy)-2-oxo-oxonan-3-yl]-4-methoxypyridine-2-carboxamide (17.0 mg, 0.037 mmol) and CH2Cl2 (0.52 mL), followed by DMAP (0.89 mg, 0.73 μmol) and TEA (10.2 μl, 0.073 mmol). Then, acetyl chloride (3.9 μl, 0.055 mmol) was added and the reaction was stirred at room temperature for 3 h. The mixture was diluted with CH2Cl2 and quenched by pouring into saturated aqueous NH4Cl. The organic phase was separated and the aqueous phase was extracted with CH2Cl2 three times. The combined organic phases were passed through a phase separator and the solvent was then evaporated. The resulting crude residue was purified by automated silica gel column chromatography (1→50% acetone/hexanes) to afford the title compound (15.7 mg, 85%) as a colorless oil.
Example 17D
Preparation of [2-[[(3S,7S,8S,9S)-7-(cyclopentoxy)-9-methyl-2-oxo-8-propoxy-oxonan-3-yl]carbamoyl]-4-methoxy-3-pyridyl]3-methoxypropanoate (F19)




To a screw-cap vial were added N-[(3S,7S,8S,9S)-7-(cyclopentoxy)-9-methyl-2-oxo-8-propoxy-oxonan-3-yl]-3-hydroxy-4-methoxypyridine-2-carboxamide (51.7 mg, 0.111 mmol) and CH2Cl2 (1.1 mL), followed by DMAP (6.8 mg, 0.056 mmol) and TEA (30.9 μl, 0.223 mmol). Then, 3-methoxypropanoyl chloride (24.1 μl, 0.223 mmol) was added dropwise and the reaction was stirred at room temperature for 3 h. The mixture was diluted with CH2Cl2 and quenched by pouring into saturated aqueous NH4Cl. The organic phase was separated and the aqueous phase was extracted with CH2Cl2 three times. The combined organic phases were passed through a phase separator and the solvent was then evaporated. The resulting crude residue was purified by automated silica gel column chromatography (1→50% acetone/hexanes) to afford the title compound (58.7 mg, 96%) as a white solid.
Example 18
Preparation of tert-butyl ((3aS,4S,7S,10aS)-4-methyl-6-oxo-2-phenyloctahydro-[1,3]dioxolo[4,5-c]oxonin-7-yl)carbamate




To a solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7,8-dihydroxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (250 mg, 0.620 mmol) in CH2Cl2 (3 mL) were added 4-methylbenzenesulfonic acid (21.34 mg, 0.124 mmol), benzaldehyde (315 μl, 3.10 mmol), and MgSO4 (100 mg), and the reaction was stirred at ambient temperature for 2 h. The reaction mixture was filtered through a plug of Celite®, concentrated and purified via silica gel chromatography (gradient, hexanes/EtOAc) to afford the title compound (240 mg, 99%) as a white solid: 1H NMR (400 MHz, CDCl3) δ 7.47 (tdd, J=5.2, 4.2, 2.8 Hz, 2H), 7.38 (dp, J=5.7, 1.5 Hz, 3H), 5.79 (s, 1H), 5.31-5.15 (m, 2H), 4.17 (ddd, J=12.4, 7.9, 5.0 Hz, 1H), 3.90 (ddd, J=11.4, 6.9, 3.0 Hz, 1H), 3.68 (dd, J=9.7, 6.9 Hz, 1H), 2.30 (ddd, J=17.7, 10.1, 4.5 Hz, 1H), 2.10-1.89 (m, 2H), 1.84-1.57 (m, 2H), 1.49 (d, J=6.3 Hz, 3H), 1.45 (s, 9H), 1.43-1.31 (m, 1H); 13C NMR (101 MHz, CDCl3) δ 173.75, 154.81, 136.32, 129.69, 128.44, 126.79, 102.84, 83.62, 80.04, 79.70, 71.69, 54.23, 34.42, 32.94, 30.94, 28.33, 19.76, 18.33; ESIMS m/z 414 ([M+H]+).
Example 19
Preparation of tert-butyl N-[(3aS,4S,7S,10aS)-2-ethyl-4-methyl-6-oxo-4,7,8,9,10,10a-hexahydro-3aH-[1,3]dioxolo[4,5-c]oxonin-7-yl]-N-tert-butoxycarbonyl-carbamate




To a solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7,8-dihydroxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (250 mg, 0.620 mmol) in CH2Cl2 (3.1 mL) were added 4-methylbenzenesulfonic acid (21.34 mg, 0.124 mmol), propionaldehyde (225 μl, 3.10 mmol), and MgSO4 (100 mg), and the reaction was stirred at ambient temperature for 2 h. The reaction mixture was filtered through a plug of Celite®, concentrated and purified via silica gel chromatography (gradient, hexanes/EtOAc) to afford the title compound (217 mg, 79%) as a sticky, colorless oil: 1H NMR (400 MHz, CDCl3) δ 4.93 (dq, J=9.6, 6.3 Hz, 1H), 4.83 (t, J=4.6 Hz, 1H), 4.67 (dd, J=12.3, 4.8 Hz, 1H), 3.69 (ddd, J=11.3, 6.8, 2.7 Hz, 1H), 3.47 (dd, J=9.6, 6.9 Hz, 1H), 2.39 (dddd, J=13.9, 12.2, 6.6, 1.6 Hz, 1H), 2.16-1.91 (m, 3H), 1.80-1.59 (m, 4H), 1.51 (s, 18H), 1.43 (d, J=6.2 Hz, 3H), 0.94 (t, J=7.6 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 171.36, 152.87, 104.15, 83.14, 82.76, 79.54, 72.13, 59.10, 34.45, 30.54, 27.97, 26.41, 21.04, 18.53, 7.93; ESIMS m/z 444 ([M+H]+).
Example 20
Preparation of A) tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-7-(3-fluorophenoxy)-8-hydroxy-9-methyl-2-oxo-oxonan-3-yl]carbamate and B) tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-8-(3-fluorophenoxy)-7-hydroxy-9-methyl-2-oxo-oxonan-3-yl]carbamate




To a solution of tris(3-fluorophenyl)bismuthine (1.056 g, 2.137 mmol) in CH2Cl2 (7.12 mL) was added peracetic acid (0.503 mL, 2.421 mmol) at 0° C., and the solution was warmed to room temperature and stirred for 20 min. To the resulting solution were added tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-7,8-dihydroxy-9-methyl-2-oxo-oxonan-3-yl]carbamate (575 mg, 1.42 mmol) and diacetoxycopper (52 mg, 0.28 mmol), and the resulting blue-green slurry was stirred at room temperature for 16 h, warmed to 40° C., and stirred at 40° C. for 4 h. The reaction mixture was filtered through a plug of Celite® and any peroxides in the filtrate were quenched by the addition of saturated aqueous sodium bisulfite (NaHSO3). The biphasic mixture was passed through a phase separator cartridge and concentrated. The crude residue was purified by silica gel chromatography (gradient, petroleum ether/MTBE) to afford the title compounds A and B.
Compound A (117 mg, 16%) was isolated as a light yellow oil: 1H NMR (400 MHz, CDCl3) δ 7.22 (td, J=8.2, 6.8 Hz, 1H), 6.74-6.61 (m, 3H), 4.95 (t, J=8.5 Hz, 1H), 4.84 (dq, J=9.5, 6.2 Hz, 1H), 4.17 (ddd, J=7.8, 6.0, 1.9 Hz, 1H), 3.86 (ddd, J=9.6, 7.6, 2.3 Hz, 1H), 2.64 (d, J=2.7 Hz, 1H), 2.29 (dddd, J=14.0, 11.2, 8.6, 1.7 Hz, 1H), 2.35-2.24 (m, 1H), 2.13-1.99 (m, 2H), 1.89 (dddd, J=17.3, 15.9, 8.6, 3.9 Hz, 1H), 1.68-1.55 (m, 1H), 1.52 (s, 18H), 1.47 (d, J=6.3 Hz, 3H); 19F NMR (376 MHz, CDCl3) δ −111.22; ESIMS m/z 498 ([M+H]+).
Compound B (214 mg, 30%) was isolated as a colorless oil: 1H NMR (400 MHz, CDCl3) δ 7.23 (td, J=8.3, 6.7 Hz, 1H), 6.83 (ddd, J=8.4, 2.5, 0.9 Hz, 1H), 6.77 (dt, J=10.8, 2.4 Hz, 1H), 6.70 (dddd, J=8.3, 7.4, 2.4, 1.2 Hz, 1H), 4.95-4.83 (m, 2H), 4.27 (dd, J=9.5, 7.8 Hz, 1H), 3.88 (ddt, J=8.1, 5.3, 2.3 Hz, 1H), 2.45-2.33 (m, 1H), 2.16-2.13 (m, 1H), 2.13-1.97 (m, 2H), 1.83 (dtd, J=12.2, 9.4, 8.2, 6.1 Hz, 2H), 1.52 (s, 18H), 1.49-1.39 (m, 1H), 1.32 (d, J=6.4 Hz, 3H); 19F NMR (376 MHz, CDCl3) δ −110.94; ESIMS m/z 498 ([M+H]+).
Example 21
Preparation of tert-butyl N-[(3S,7S,8S,9S)-8-(4-bromophenoxy)-9-methyl-2-oxo-7-propoxy-oxonan-3-yl]-N-tert-butoxycarbonyl-carbamate




To a solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-2-oxo-8-phenoxy-7-propoxy-oxonan-3-yl]carbamate (523 mg, 1.003 mmol) in CH2Cl2 (5 mL) was added NBS (357 mg, 2.005 mmol). The vial was wrapped in aluminum foil and stirred at room temperature for 16 h. An additional portion of NBS (357 mg, 2 mmol) was added and the reaction was stirred at room temperature for an additional 3 h, concentrated, and the residue purified by silica gel chromatography (gradient, hexanes/EtOAc) to afford the title compound (567 mg, 94%): 1H NMR (400 MHz, CDCl3) δ 7.39-7.30 (m, 2H), 7.00-6.91 (m, 2H), 4.90-4.78 (m, 2H), 4.28 (dd, J=9.7, 7.3 Hz, 1H), 3.52 (ddd, J=7.2, 5.2, 1.9 Hz, 1H), 3.44 (dt, J=9.0, 6.6 Hz, 1H), 3.20 (dt, J=9.0, 6.5 Hz, 1H), 2.48-2.33 (m, 1H), 2.23-2.11 (m, 1H), 2.12-2.00 (m, 1H), 1.82-1.65 (m, 2H), 1.52 (s, 18H), 1.47-1.36 (m, 2H), 1.31 (d, J=6.4 Hz, 3H), 1.12-0.99 (m, 1H), 0.77 (t, J=7.4 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 170.80, 158.94, 152.87, 132.12, 118.28, 113.38, 83.31, 82.96, 82.76, 72.40, 71.28, 57.34, 30.53, 27.98, 23.15, 19.23, 18.17, 10.56; ESIMS m/z 622 ([M+H]+).
Example 22
Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-9-methyl-2-oxo-8-(4-phenylphenoxy)-7-propoxy-oxonan-3-yl]carbamate




A vial was charged with tert-butyl N-[(3S,7S,8S,9S)-8-(4-bromophenoxy)-9-methyl-2-oxo-7-propoxy-oxonan-3-yl]-N-tert-butoxycarbonyl-carbamate (34 mg, 0.057 mmol), phenylboronic acid (19 mg, 0.156 mmol), Na2CO3 (18.0 mg, 0.170 mmol) and Pd(PPh3)4 (6.54 mg, 5.66 μmol). The vial was evacuated and backfilled with N2 (repeated 3×), dioxane (425 μl) and water (142 μl) were added, and the vial was fitted with an air condenser and the reaction mixture was heated at 80° C. for 3 h. The cooled reaction mixture was diluted with CH2Cl2, passed through a phase separator cartridge, concentrated, and the residue purified by silica gel chromatography (gradient, hexanes/EtOAc) to afford the title compound (25 mg, 74%) as a white solid: 1H NMR (400 MHz, CDCl3) δ 7.59-7.53 (m, 2H), 7.51-7.46 (m, 2H), 7.47-7.37 (m, 2H), 7.36-7.26 (m, 1H), 7.18-7.09 (m, 2H), 4.94-4.79 (m, 2H), 4.40 (dd, J=9.6, 7.3 Hz, 1H), 3.56 (ddd, J=7.1, 5.1, 1.9 Hz, 1H), 3.47 (dt, J=9.0, 6.6 Hz, 1H), 3.26 (dt, J=9.1, 6.5 Hz, 1H), 2.49-2.35 (m, 1H), 2.25-2.12 (m, 1H), 2.13-2.01 (m, 1H), 1.86-1.66 (m, 2H), 1.52 (s, 18H), 1.48-1.39 (m, 2H), 1.37 (d, J=6.3 Hz, 3H), 1.08 (ddt, J=15.9, 7.5, 1.9 Hz, 1H), 0.77 (t, J=7.4 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 170.86, 159.35, 152.89, 140.82, 134.28, 128.69, 127.99, 126.74, 126.66, 116.75, 83.07, 83.04, 82.75, 72.67, 71.42, 57.42, 30.59, 28.76, 27.99, 23.19, 19.30, 18.26, 10.57; ESIMS m/z 620 ([M+Na]+).
Example 23
Preparation of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-methoxy-9-methyl-7-(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamate




To a solution of a tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8S,9S)-8-hydroxy-9-methyl-7-(2-methylallyloxy)-2-oxo-oxonan-3-yl]carbamate (1.00 g, 2.19 mmol) in CH2Cl2 (21.86 ml) at 0° C. was added Proton Sponge® (0.937 g, 4.37 mmol) followed by trimethyloxonium tetrafluoroborate (0.485 g, 3.28 mmol). The mixture was stirred at 0° C. for 30 min, warmed to ambient temperature, stirred for an additional 30 min, and then poured into sat. aqueous NaHCO3 (50 mL) and extracted with CH2Cl2 (3×50 mL). The combined organic extracts were washed with 10% NaHSO4 (2×50 mL), washed with brine (50 mL), and dried by passing through a phase-separation cartridge. The filtrate was concentrated and the crude foam was purified via flash chromatography (SiO2, 0→35% EtOAc/hexane) to afford the title product as a clear oil (1.03 g, 100%): 1H NMR (400 MHz, CDCl3) δ 4.98 (dd, J=2.0, 0.9 Hz, 1H), 4.91-4.85 (m, 1H), 4.82 (dd, J=10.4, 8.1 Hz, 1H), 4.62 (dq, J=9.7, 6.3 Hz, 1H), 3.98 (d, J=12.1 Hz, 1H), 3.86 (d, J=12.1 Hz, 1H), 3.56 (s, 3H), 3.40 (ddd, J=7.0, 5.1, 1.7 Hz, 1H), 3.27 (dd, J=9.6, 7.3 Hz, 1H), 2.43-2.29 (m, 1H), 2.17-1.97 (m, 2H), 1.77 (s, 3H), 1.74-1.58 (m, 2H), 1.51 (s, 18H), 1.39 (d, J=6.3 Hz, 3H), 1.01-0.88 (m, 1H); 13C NMR (101 MHz, CDCl3) δ 170.84, 152.88, 142.53, 112.15, 85.57, 83.24, 82.65, 73.03, 72.89, 61.32, 57.36, 30.55, 28.40, 27.96, 19.57, 19.17, 17.87; HRMS-ESI (m/z) [M+Na]+ calcd for C24H41NNaO8, 494.2734; found, 494.2724.
Example A
Evaluation of Fungicidal Activity: Leaf Blotch of Wheat (Mycosphaerella graminicola; Anamorph: Septoria tritici; Bayer Code SEPTTR)
Technical grades of materials were dissolved in acetone, which were then mixed with nine volumes of water containing 110 ppm Triton X-100. The fungicide solutions were applied onto wheat seedlings using an automated booth sprayer to run-off. All sprayed plants were allowed to air dry prior to further handling. All fungicides were evaluated using the aforementioned method for their activity vs. all target diseases. Wheat leaf blotch and brown rust activity were also evaluated using track spray applications, in which case the fungicides were formulated as EC formulations, containing 0.1% Trycol 5941 in the spray solutions.
Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soil/50% soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension of Septoria tritici either prior to or after fungicide treatments. After inoculation the plants were kept in 100% relative humidity (one day in a dark dew chamber followed by two to three days in a lighted dew chamber at 20° C.) to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 20° C. for disease to develop. When disease symptoms were fully expressed on the 1st leaves of untreated plants, infection levels were assessed on a scale of 0 to 100 percent disease severity. Percent disease control was calculated using the ratio of disease severity on treated plants relative to untreated plants.
Example B
Evaluation of Fungicidal Activity: Wheat Brown Rust (Puccinia triticina; Synonym: Puccinia recondite f. sp. tritici; Bayer Code PUCCRT)
Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soil/50% soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension of Puccinia triticina either prior to or after fungicide treatments. After inoculation the plants were kept in a dark dew room at 22° C. with 100% relative humidity overnight to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 24° C. for disease to develop. Fungicide formulation, application and disease assessment followed the procedures as described in the Example A.
Example C
Evaluation of Fungicidal Activity: Wheat Glume Blotch (Leptosphaeria nodorum; Bayer Code LEPTNO)
Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soil/50% soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension of Leptosphaeria nodorum 24 hr after fungicide treatments. After inoculation the plants were kept in 100% relative humidity (one day in a dark dew chamber followed by two days in a lighted dew chamber at 20° C.) to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 20° C. for disease to develop. Fungicide formulation, application and disease assessment followed the procedures as described in the Example A.
Example D
Evaluation of Fungicidal Activity: Apple Scab (Venturia inaequalis; Bayer Code VENTIN)
Apple seedlings (variety McIntosh) were grown in soil-less Metro mix, with one plant per pot. Seedlings with two expanding young leaves at the top (older leaves at bottom of the plants were trimmed) were used in the test. Plants were inoculated with a spore suspension of Venturia inaequalis 24 hr after fungicide treatment and kept in a 22° C. dew chamber with 100% RH for 48 hr, and then moved to a greenhouse set at 20° C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.
Example E
Evaluation of Fungicidal Activity: Grape Powdery Mildew (Uncinula necator; Bayer Code UNCINE)
Grape seedlings (variety Carignane) were grown in soil-less Metro mix, with one plant per pot, and used in the test when approximately one month old. Plants were inoculated 24 hr after fungicide treatment by shaking spores from infected leaves over test plants. Plants were maintained in a greenhouse set at 20° C. until disease was fully developed. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.
Example F
Evaluation of Fungicidal Activity: Powdery Mildew of Cucumber (Erysiphe cichoracearum; Bayer Code ERYSCI)
Cucumber seedlings (variety Bush Pickle) were grown in soil-less Metro mix, with one plant per pot, and used in the test when 12 to 14 days old. Plants were inoculated with a spore suspension 24 hr following fungicide treatments. After inoculation the plants remained in the greenhouse set at 20° C. until disease was fully expressed. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.
Example G
Evaluation of Fungicidal Activity: Leaf Spot of Sugar Beets (Cercospora beticola; Bayer Code CERCBE)
Sugar beet plants (variety HH88) were grown in soil-less Metro mix and trimmed regularly to maintain a uniform plant size prior to test. Plants were inoculated with a spore suspension 24 hr after fungicide treatments. Inoculated plants were kept in a dew chamber at 22° C. for 48 hr then incubated in a greenhouse set at 24° C. under a clear plastic hood with bottom ventilation until disease symptoms were fully expressed. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.
Example H
Evaluation of Fungicidal Activity: Asian Soybean Rust (Phakopsora pachyrhizi; Bayer Code PHAKPA)
Technical grades of materials were dissolved in acetone, which were then mixed with nine volumes of water containing 0.011% Tween 20. The fungicide solutions were applied onto soybean seedlings using an automated booth sprayer to run-off. All sprayed plants were allowed to air dry prior to further handling.
Soybean plants (variety Williams 82) were grown in soil-less Metro mix, with one plant per pot. Two weeks old seedlings were used for testing. Plants were inoculated either 3 days prior to or 1 day after fungicide treatments. Plants were incubated for 24 h in a dark dew room at 22° C. and 100% RH then transferred to a growth room at 23° C. for disease to develop. Disease severity was assessed on the sprayed leaves.
Example I
Evaluation of Fungicidal Activity: Wheat Powdery Mildew (Blumeria graminis f. sp. tritici; Synonym: Erysiphe graminis f. sp. tritici; Bayer Code ERYSGT)
Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soil/50% soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated by dusting with infected stock plants 24 hr after fungicide treatments. After inoculation the plants were kept in a greenhouse set at 20° C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.
Example J
Evaluation of Fungicidal Activity: Barley Powdery Mildew (Blumeria graminis f. sp. hordei; Synonym: Erysiphe graminis f. sp. hordei; Bayer Code ERYSGH)
Barley seedlings (variety Harrington) were propagated in soil-less Metro mix, with each pot having 8 to 12 plants, and used in the test when first leaf was fully emerged. Test plants were inoculated by dusting with infected stock plants 24 hr after fungicide treatments. After inoculation the plants were kept in a greenhouse set at 20° C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.
Example K
Evaluation of Fungicidal Activity: Barley Scald (Rhyncosporium secalis; Bayer Code RHYNSE)
Barley seedlings (variety Harrington) were propagated in soil-less Metro mix, with each pot having 8 to 12 plants, and used in the test when first leaf was fully emerged. Test plants were inoculated by an aqueous spore suspension of Rhyncosporium secalis 24 hr after fungicide treatments. After inoculation the plants were kept in a dew room at 20° C. with 100% relative humidity for 48 hr. The plants were then transferred to a greenhouse set at 20° C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.
Example L
Evaluation of Fungicidal Activity: Rice Blast (Magnaporthe grisea; Anamorph: Pyricularia oryzae; Bayer Code PYRIOR)
Rice seedlings (variety Japonica) were propagated in soil-less Metro mix, with each pot having 8 to 14 plants, and used in the test when 12 to 14 days old. Test plants were inoculated with an aqueous spore suspension of Pyricularia oryzae 24 hr after fungicide treatments. After inoculation the plants were kept in a dew room at 22° C. with 100% relative humidity for 48 hr to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 24° C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.
Example M
Evaluation of Fungicidal Activity: Tomato Early Blight (Alternaria solani; Bayer Code ALTESO)
Tomato plants (variety Outdoor girl) were propagated in soil-less Metro mix, with each pot having one plant, and used when 12 to 14 days old. Test plants were inoculated with an aqueous spore suspension of Alternaria solani 24 hr after fungicide treatments. After inoculation the plants were kept in 100% relative humidity (one day in a dark dew chamber followed by two to three days in a lighted dew chamber at 20° C.) to permit spores to germinate and infect the leaf. The plants were then transferred to a growth room at 22° C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.
Example N
Evaluation of Fungicidal Activity: Cucumber Anthracnose (Glomerella lagenarium; Anamorph: Colletotrichum lagenarium; Bayer Code COLLLA)
Cucumber seedlings (variety Bush Pickle) were propagated in soil-less Metro mix, with each pot having one plant, and used in the test when 12 to 14 days old. Test plants were inoculated with an aqueous spore suspension of Colletotrichum lagenarium 24 hr after fungicide treatments. After inoculation the plants were kept in a dew room at 22° C. with 100% relative humidity for 48 hr to permit spores to germinate and infect the leaf. The plants were then transferred to a growth room set at 22° C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.







TABLE 1







Structure and Preparation Method for F Series Compounds











Prepared




According


Compound

to


Number
Structure
Example





F1




11


 


F2




12, 12A


 


F3




12, 12B (1-3)


 


F4




12, 12B (1-3)


 


F5




12, 12C (1-2)


 


F6




12, 12A


 


F7




13, 13B (1-3)


 


F8




13, 13B (1) And 13D (1, 2)


 


F9




13, 13B (1) and 13D (1-2)


 


F10




13, 13E (1-3)


 


F11




13, 13F (1-3)


 


F12




14, 14A


 


F13




15 (1-4)


 


F14




16A


 


F15




17A


 


F16




17B


 


F17




17C


 


F18




17D


 


F19




16A


 


F20




17A


 


F21




16B


 


F22




16B


 


F23




16B


 


F24




16B


 


F25




16B


 


F26




17A


 


F27




16A


 


F28




17A


 


F29




17A


 


F30




17A


 


F31




17A


 


F32




17A


 


F33




16A


 


F34




17B


 


F35




17B


 


F36




17B


 


F37




17B


 


F38




17B


 


F39




17A


 


F40




16A


 


F41




16A


 


F42




17C


 


F43




17A


 


F44




17A


 


F45




17A


 


F46




17A


 


F47




17C


 


F48




17A


 


F49




17B


 


F50




16A


 


F51




17B


 


F52




17B


 


F53




16A


 


F54




16A


 


F55




16A


 


F56




16A


 


F57




16A


 


F58




17C


 


F59




17A


 


F60




17A


 


F61




17A


 


F62




17B


 


F63




17A


 


F64




16A


 


F65




16A


 


F66




17A


 


F67




17B


 


F68




17A


 


F69




17B


 


F70




16A


 


F71




16A


 


F72




17A


 


F73




16A


 


F74




16A


 


F75




16A


 


F76




17B


 


F77




17C


 


F78




17A


 


F79




17B


 


F80




17A


 


F81




17C


 


F82




16A


 


F83




17C


 


F84




16A


 


F85




16A


 


F86




17A


 


F87




17A


 


F88




17A


 


F89




17C


 


F90




17C


 


F91




17C


 


F92




17C


 


F93




16A


 


F94




16A


 


F95




17A


 


F96




17A


 


F97




17B


 


F98




17B


 


F99




17B


 


F100




17B


 


F101




17B


 


F102




17C


 


F103




17C


 


F104




16A


 


F105




16A


 


F106




17A


 


F107




17A


 


F108




17B


 


F109




17C


 


F110




17D


 


F111




16A


 


F112




17B


 


F113




16A


 


F114




16A


 


F115




17A


 


F116




17A


 


F117




16A


 


F118




16A


 


F119




16A


 


F120




16A


 


F121




17A


 


F122




17A


 


F123




17B


 


F124




17B


 


F125




17A


 


F126




17B


 


F127




16A


 


F128




16A


 


F129




16A


 


F130




17A


 


F131




17C


 


F132




17D


 


F133




17A


 


F134




17C


 


F135




17A


 


F136




17B


 


F137




17C


 


F138




17A


 


F139




17B


 


F140




17D


 


F141




17C


 


F142




16A


 


F143




16A


 


F144




17A


 


F145




17B


 


F146




17D


 


F147




17D


 


F148




17A


 


F149




16A


 


F150




17A


 


F151




17C


 


F152




17D


 


F153




16A


 


F154




17B


 


F155




17A


 


F156




16A


 


F157




17B


 


F158




17A


 


F159




17C


 


F160




16A


 


F161




17B


 


F162




17A


 


F163




16A


 


F164




16A


 


F165




17A


 


F166




17A


 


F167




16A


 


F168




16A


 


F169




17B


 


F170




17A


 


F171




17B


 


F172




17A


 


F173




17C


 


F174




13, 13F (1-3)


 


F175




13, 13F (1-3)


 


F176




13, 13F (1-3)


 


F177




12, 12C (1-2)


 


F178




12, 12B (1-3)


 


F179




12, 12B (1-3)


 


F180




13, 13B (1)


 


F181




13, 13B (1) and 13F (1, 3)


 


F182




12, 12C (1-2)


 


F183




12, 12B (1-3)


 


F184




13, 13F (1-3) or 13A (1-2)


 


F185




13, 13C (1-3)


 


F186




13, 13B (1-3)


 


F187




13, 13A (1-2)


 


F188




12, 12B (1-3)


 


F189




12, 12B (1-3)


 


F190




13, 13A (2)


 


F191




12, 12B (1, 3)


 


F192




12, 12B (1-3)


 


F193




12, 12B (1-3)


 


F194




12, 12A


 


F195




12, 12B (1-3)


 


F196




12, 12B (1-3)


 


F197




12, 12B (1-3)


 


F198




13, 13F (1-3)


 


F199




13, 13F (1-3)


 


F200




13, 13G (1-3)


 


F201




13, 13B (1) and 13D (1-2)


 


F202




13, 13B (1) and 13D (1-2)


 


F203




13, 13A (1-2)


 


F204




13, 13G (1-3)


 


F205




13, 13B (1) and 13D (1-2)


 


F206




12, 12B (1-3)


 


F207




13, 13F (1-3)


 


F208




13, 13F (1-3)


 


F209




13, 13G (1-3)


 


F210




16A


 


F211




16A


 


F212




16A


 


F213




16A


 


F214




17C


 


F215




17D


 


F216




17C


 


F217




17A


 


F218




17B


 


F219




16A


 


F220




16A


 


F221




16A


 


F222




17A


 


F223




17A


 


F224




16A


 


F225




17A


 


F226




13, 13B (1) and 13F (1, 3)


 


F227




13, 13G (1-3)


 


F228




13, 13G (1-3)


 


F229




12, 12B (1-3)


 


F230




13, 13G (1-3)


 


F231




12, 13D (1-2)


 


F232




16A


 


F233




17A


 


F234




17B


 


F235




17C


 


F236




17C


 


F237




17B


 


F238




12, 13D (1-2)


 


F239




16A


 


F240




17A


 


F241




17B


 


F242




17C


 


F243




17D


 


F244




13, 23, 12A


 


F245




16A


 


F246




13, 23, 13B (1, 3)


 


F247




16A


 


F248




12, 23, 12A


 


F249




16A


 


F250




17A


 


F251




17A


 


F252




17A


 


F253




17B


 


F254




17B


 


F255




17B


 


F256




17C


 


F257




17C


 


F258




17C


 


F259




17D


 


F260




17D


 


F261




12, 12B (1-3)


 


F262




16A


 


F263




12, 12B (1-3)


 


F264




16A


 


F265




17A


 


F266




17C


 


F267




17A


 


F268




12, 12B (1-3)


 


F269




20, 12B (1-3)


 


F270




16A


 


F271




16A


 


F272




16A


 


F273




16A


 


F274




17C


 


F275




17C


 


F276




12, 12B (1-3)


 


F277




12, 12B (1-2), 21, 12A


 


F278




20, 12B (1-3)


 


F279




12, 12B (1-3)


 


F280




16A


 


F281




16A


 


F282




17C


 


F283




16A


 


F284




17C


 


F285




17C


 


F286




17C


 


F287




17C


 


F288




16A


 


F289




17C


 


F290




16A


 


F291




17C


 


F292




12, 12B (1-2), 21, 22 12A


 


F293




12, 12B (1-3)


 


F294




12, 12B (1-2), 21, 22 12A
















TABLE 2







Analytical Data for F Series Compounds

















*Mass.

*13C NMR;


*Cmpd. No.
*Phys. Apps.
*MP
*IR
Spec.
*1H NMR
*19F NMR





F1
White
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Crystalline


(m/z)
4.84 (dd, J = 10.0,
(CDCl3) δ



Solid


[M + Na]+
7.4 Hz, 1H), 4.72 (dq,
170.82,






calcd for
J = 9.1, 6.3 Hz, 1H),
152.88, 82.85,






C19H33NNaO8,
3.59-3.41 (m, 2H),
73.79, 73.28,






426.2102;
2.70-2.58 (m, 1H),
57.70, 35.10,






found,
2.42-2.27 (m, 1H),
30.87, 29.22,






426.2098
2.12-2.00 (m, 1H),
27.95, 19.98,







1.96-1.63 (m, 3H),
18.06







1.59-1.46 (m, 18H),








1.42 (d, J = 6.3 Hz,








3H)



F2
White Foam
—
—
ESI-MS
1H NMR (CDCl3) δ
13C NMR






m/z 356.5
8.74 (s, 3H),
(CDCl3) δ






([M + H]+)
7.20 (dd, J = 15.3, 7.6 Hz,
170.00,







4H), 7.01 (d, J = 8.0 Hz,
159.33,







2H), 6.92 (dt, J = 14.2,
157.42,







7.3 Hz, 2H),
129.47,







6.81 (d, J = 8.0 Hz,
129.46,







2H), 1.90-1.64 (m,
121.76,







3H), 5.08 (t, J = 7.0 Hz,
121.59,







1H), 4.60 (t, J = 8.1 Hz,
116.69,







1H), 4.50 (br
116.48, 82.15,







s, 1H), 4.16 (br s,
81.87, 73.49,







1H), 2.57 (br s, 1H),
52.29, 30.92,







2.30 (br s, 1H),
28.28, 18.11,







1.38 (d, J = 5.7 Hz, 3H),
17.88







1.13 (d, J = 10.0 Hz,








1H)



F3
White Solid
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.73 (br s, 3H),
(CDCl3) δ






[M + H]+
7.28-7.21 (m, 2H),
170.08,






calcd for
7.04 (d, J = 7.9 Hz, 2H),
159.50,






C19H30NO4,
6.94 (t, J = 7.3 Hz,
129.35,






336.2169;
1H), 4.98 (dq, J = 12.7,
121.39,






found,
6.1 Hz, 1H),
116.34, 82.82,






336.2173
4.37 (dd, J = 9.3, 7.4 Hz,
82.50, 76.39,







1H), 4.11 (t, J = 8.3 Hz,
73.64, 52.28,







1H), 3.70 (s,
31.07, 28.67,







1H), 3.22 (dd, J = 8.7,
27.87, 19.33,







6.6 Hz, 1H),
19.18, 18.00,







3.03 (dd, J = 8.7, 6.2 Hz,
17.87







1H), 2.58 (s, 1H),








2.28-2.15 (m, 1H),








1.90-1.59 (m, 4H),








1.34 (d, J = 6.3 Hz,








3H), 0.98 (d, J = 9.3 Hz,








1H), 0.77 (d, J = 6.7 Hz,








3H), 0.72 (d,








J = 6.7 Hz, 3H)



F4
White Solid
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.65 (br s, 3H),
(CDCl3) δ






[M + H]+
7.25 (t, J = 7.9 Hz, 2H),
170.02,






calcd for
7.00-6.84 (m, 3H),
157.44,






C19H30NO4,
4.93-4.68 (m, 1H),
129.50,






336.2169;
4.34 (br s, 1H),
121.27,






found,
4.09 (br s, 1H),
116.49, 83.14,






336.2167
3.61-3.46 (m, 2H),
82.78, 80.70,







3.36 (dd, J = 8.5, 6.7 Hz,
73.85, 52.21,







1H), 2.49 (br s, 1H),
30.85, 28.97,







1.89-1.51 (m, 4H),
28.16, 19.37,







1.43 (d, J = 6.0 Hz,
19.27, 17.91,







3H), 1.05-0.87 (m,
17.76







1H), 0.82 (d, J = 6.7 Hz,








3H), 0.78 (d, J = 6.7 Hz,








3H)



F5
Colorless
—
—
ESIMS
1H NMR (CDCl3)
13C NMR



Solid


m/z 404.2
δ 8.65 (bs, 3H),
(CDCl3) δ






([M + H]+)
7.02-6.86 (m, 4H),
170.11,







6.82-6.67 (m, 4H),
157.86 (d, J = 239.9 Hz),







5.07-4.96 (m, 1H),
155.67 (d, J = 2.0 Hz),







4.44 (dd, J = 9.4, 7.3 Hz,
154.77,







1H), 4.34-4.26 (m,
151.39,







1H), 4.21-4.08 (m,
118.40,







1H), 3.70 (s, 3H),
117.88 (d, J = 8.1 Hz),







3.38-3.04 (m, 1H),
115.97 (d, J = 23.0 Hz),







2.63-2.51 (m, 1H),
114.74, 83.58,







2.30-2.13 (m, 1H),
83.43, 73.46,







1.85-1.69 (m, 2H),
55.72, 52.40,







1.37 (d, J = 6.3 Hz,
31.01, 28.32,







3H), 1.10-0.98 (m,
18.19, 18.02;







1H)
19F NMR








(CDCl3) δ −122.33


F6
Chalky
188-230
—
ESIMS
1H NMR (CDCl3) δ
—



White Solid


m/z 316.6
8.69 (s, 2H), 4.75 (s,







([M + H]+)
1H), 4.00 (s, 1H),








3.60 (dd, J = 8.6, 6.2 Hz,








1H),








3.36-3.28 (m, 3H),








3.28-3.20 (m, 1H), 3.09 (dd, J = 8.6,








6.3 Hz, 1H),








2.51 (s, 1H), 2.13 (s, 1H),








1.88-1.52 (m, 6H),








1.39 (d, J = 6.2 Hz,








3H), 0.96-0.85 (m,








12H)



F7
White Solid
199-202
3395,
HRMS-ESI
1H NMR (CD3OD) δ
13C NMR





2947,
(m/z)
7.07-6.94 (m, 2H),
(CD3OD) δ





2093,
[M + H]+
6.90-6.71 (m, 2H),
169.76,





1745,
calcd for
5.01 (dq, J = 9.4, 6.4 Hz,
154.43,





1506
C20H32NO5,
1H), 4.32 (dd, J = 9.5,
153.69,






366.2275;
7.3 Hz, 1H),
117.00,






found,
3.98 (dd, J = 10.8, 7.5 Hz,
114.06, 82.99,






366.2275
1H), 3.74 (s, 3H),
82.91, 76.03,







3.64-3.48 (m, 1H),
73.61, 54.67,







3.30-3.27 (m, 1H),
51.40, 30.61,







3.08 (dd, J = 8.8, 6.1 Hz,
28.58, 27.32,







1H),
18.35, 18.23,







2.40-2.18 (m, 2H),
17.41, 17.02







1.89-1.71 (m, 2H), 1.65 (dq, J = 13.2,








6.6 Hz, 1H),








1.56-1.42 (m, 1H),








1.36 (d, J = 6.4 Hz,








3H), 0.95 (dd, J = 11.5,








7.3 Hz, 1H),








0.78 (dd, J = 16.4,








6.7 Hz, 6H)



F8
White Solid
—
—
ESIMS
—
—






m/z 356.3








([M + H]+)




F9
White Solid
—
—
ESIMS
1H NMR (CD3OD) δ
13C NMR






m/z 356
5.11 (dd, J = 9.7, 7.9 Hz,
(CD3OD) δ






([M + H]+)
1H), 4.99 (dq, J = 9.7,
177.44,







6.3 Hz, 1H),
171.22, 82.37,







3.99 (dd, J = 10.8, 7.5 Hz,
77.16, 76.44,







1H), 3.46 (ddd, J = 7.4,
73.86, 52.81,







5.1, 1.8 Hz, 1H),
45.17, 31.99,







3.37-3.32 (m, 1H),
31.11, 30.86,







3.02 (dd, J = 8.7, 6.5 Hz,
30.01, 28.36,







1H),
26.78, 26.69,







2.87-2.73 (m, 1H),
19.77, 19.72,







2.37-2.20 (m, 2H),
18.51, 17.57







1.99-1.55 (m, 12H),








1.55-1.41 (m, 1H), 1.27 (d, J = 6.3 Hz,








3H),








0.92 (dtd, J = 15.1, 4.8,








2.4 Hz, 1H), 0.86 (dd,








J = 6.7, 1.2 Hz, 6H)



F10
White Solid
231-235
2944,
HRMS-ESI
1H NMR (CD3OD) δ
13C NMR





2870,
(m/z)
5.13 (dd, J = 9.8, 7.8 Hz,
(CD3OD) δ





2106,
[M + Na]+
1H),
174.56,





1742,
calcd for
5.08-4.96 (m, 1H), 4.01 (dd, J = 10.7,
169.88, 81.00,





1727,
C17H29NNaO5,
7.5 Hz, 1H),
75.96, 75.24,





1225
350.1938;
3.49 (ddd, J = 7.6,
72.42, 51.38,






found,
5.2, 1.8 Hz, 1H),
30.64, 28.52,






350.1937
3.38 (dd, J = 8.8, 6.0 Hz,
27.12, 18.29,







1H), 3.05 (dd, J = 8.8,
18.21, 17.08,







6.7 Hz, 1H),
16.01, 12.23,







2.44-2.20 (m, 2H),
7.69, 7.57







1.86-1.61 (m, 4H),








1.59-1.42 (m, 1H),








1.30 (d, J = 6.3 Hz, 3H),








1.02-0.90 (m, 5H),








0.90 (dd, J = 6.6, 2.3 Hz,








6H)



F11
White Solid
236-240
2943,
—
1H NMR (CD3OD) δ
13C NMR





2900,

4.87-4.75 (m, 1H),
(CD3OD) δ





2872,

3.97-3.80 (m, 2H),
169.81, 83.65,





2109,

3.71 (dt, J = 9.3, 6.2 Hz,
83.58, 75.37,





1743,

1H),
73.68, 71.34,





1453,

3.43-3.35 (m, 3H), 3.14 (dd, J = 8.7,
51.39, 30.56,





1253

6.0 Hz, 1H),
30.21 (q, J = 28.7 Hz),







2.33-2.12 (m, 4H),
28.74, 26.95,







1.89-1.72 (m, 3H),
22.90-22.61 (m), 18.51,







1.68 (dq, J = 9.5, 4.6 Hz,
18.39, 17.35,







2H), 1.52-1.35 (m,
16.81;







4H), 0.93 (dd, J = 6.7,
19F NMR







3.7 Hz, 6H),
(CD3OD) δ







0.85 (dt, J = 16.3, 4.8 Hz,
−69.61 (t, J = 11.3 Hz)







1H)



F12
Flaky
—
3455,
HRMS-ESI
1H NMR (CD3OD) δ
13C NMR



Brown Solid

2951,
(m/z)
5.21 (dd, J = 9.7, 8.0 Hz,
(CD3OD) δ





2870,
[M + H]+
1H), 5.14 (dq, J = 9.7,
175.65,





1732,
calcd for
6.2 Hz, 1H),
169.83, 74.39,





1184,
C21H34NO6,
5.03 (ddd, J = 7.7, 5.4, 2.2 Hz,
73.59, 72.07,





1144
396.2381;
1H), 4.03 (t, J = 9.1 Hz,
51.35, 43.64,






found,
1H),
43.52, 30.54,






396.2372
2.73 (dtt, J = 24.0, 8.7, 6.9 Hz,
29.57, 29.53,







2H), 2.30 (dt, J = 13.9,
29.44, 28.72,







7.1 Hz, 1H),
25.31, 25.25,







2.21-2.08 (m, 1H),
17.29, 16.10







1.95-1.54 (m, 18H),








1.48 (q, J = 12.6,








12.1 Hz, 1H), 1.30 (d,








J = 6.2 Hz, 3H),








1.15 (ddt, J = 16.3, 7.6,








2.4 Hz, 1H)



F13
Greasy
—
2955,
HRMS-ESI
—
13C NMR



White Solid

2873,
(m/z)

(CD3OD) δ





1748,
[M + H]+

169.78,





1223,
calcd for

169.75, 85.14,





1103
C18H36NO5,

83.88, 83.69,






346.2588;

83.42, 75.56,






found,

75.48, 75.46,






346.2596

73.85, 73.66,








73.09, 60.22,








51.39, 32.19,








30.53, 28.75,








28.72, 27.28,








27.26, 27.17,








19.04, 18.44,








18.41, 17.39,








16.77, 16.63,








12.88


F14
White Foam
—
3373,
ESIMS
1H NMR (CDCl3) δ
13CNMR





2923,
m/z 463.3
12.08 (s, 1H),
(CDCl3) δ





2853,
([M + H]+);
8.47 (d, J = 8.1 Hz, 1H),
172.12,





1740,
HRMS-ESI
7.99 (d, J = 5.1 Hz,
168.78,





1650,
(m/z)
1H), 6.87 (d, J = 5.2 Hz,
155.47,





1575,
[M + H]+
1H), 4.97 (dq, J = 2.8,
148.84,





1527,
calcd for
1.4 Hz, 2H),
142.56,





1448,
C24H34N2O7,
4.87 (dq, J = 4.7, 2.2 Hz,
142.50,





1441
463.2433;
2H), 4.90-4.82 (m,
140.65,






found,
1H), 4.60 (dt, J = 10.8,
130.50,






463.2439
7.6 Hz, 1H),
112.25,







4.28 (d, J = 11.7 Hz,
112.12,







1H), 4.05 (d, J = 11.7 Hz,
109.60, 83.77,







1H), 3.97 (d, J = 12.4 Hz,
83.62, 73.30,







1H), 3.94 (s,
73.24, 56.20,







3H), 3.85 (d, J = 11.6 Hz,
51.43, 33.42,







1H),
29.54, 28.08,







3.57-3.42 (m, 2H), 2.38 (dtd, J = 13.7,
19.93, 19.81,







7.1, 6.7, 1.8 Hz,
18.40, 18.12







1H),








2.09-2.20 (m, 1H),








1.79-1.74 (m, 6H),








1.75-1.66 (m, 1H),








1.61-1.54 (m, 2H),








1.49-1.37 (m, 3H),








0.90-0.80 (m, 1H);



F15
Colorless
—
3377,
HRMS-ESI
1H NMR (CDCl3) δ
13CNMR



Oil

2924,
(m/z)
8.32 (d, J = 8.1 Hz,
(CDCl3) δ





2854,
[M + H]+
1H), 8.28 (dd, J = 5.3,
172.59,





1745,
calcd for
1.8 Hz, 1H), 6.95 (d,
170.26,





1676,
C27H39N2O9,
J = 5.3 Hz, 1H),
162.96,





1502
535.2650;
5.74 (d, J = 1.7 Hz, 2H),
160.25,






found,
4.97 (s, 2H), 4.87 (d,
145.72,






535.2644
J = 2.6 Hz, 2H),
143.95,







4.85-4.79 (m, 1H),
142.46,







4.61 (dt, J = 10.1, 7.6 Hz,
142.40,







1H), 4.28 (d, J = 11.7 Hz,
142.38,







1H), 4.05 (d, J = 11.7 Hz,
112.08,







1H), 3.95 (d,
111.94,







J = 12.1 Hz, 1H),
109.61, 89.50,







3.91 (s, 3H), 3.85 (d,
83.69, 83.56,







J = 11.6 Hz, 1H),
73.07, 72.88,







3.51-3.45 (m, 2H),
56.18, 51.62,







2.38 (dt, J = 13.6, 6.8 Hz,
33.35, 29.41,







1H),
28.01, 20.86,







2.21-2.08 (m, 1H), 2.07 (s, 3H),
19.79, 19.68,







1.75 (s, 6H),
18.33, 17.97







1.74-1.61 (m, 1H), 1.56 (d,








J = 3.6 Hz, 1H),








1.42 (d, J = 6.5 Hz, 3H),








1.40-1.29 (m, 1H),








1.03-0.79 (m, 1H)



F16
Colorless
—
3377,
HRMS-ESI
1H NMR (CDCl3) δ
13CNMR



Oil

2974,
(m/z)
8.37 (d, J = 8.0 Hz,
(CDCl3) δ





2934,
[M + H]+
1H), 8.27 (d, J = 5.1 Hz,
176.24,





1744,
calcd for
1H), 6.94 (d, J = 5.3 Hz,
172.60,





1677,
C27H39N2O9,
1H),
162.94,





1503,
563.2963;
5.79-5.74 (m, 2H), 4.97 (s,
160.23,





1455
found,
2H), 4.89-4.81 (m,
145.59,






563.2974
1H), 4.87-4.79 (s,
144.19,







2H), 4.61 (q, J = 8.0 Hz,
142.47,







1H), 4.27 (d, J = 11.6 Hz,
142.42,







1H),
142.06,







4.04 (d, J = 11.7 Hz, 1H),
112.08,







3.96 (d, J = 12.0 Hz,
111.95,







1H), 3.89 (s, 3H),
109.54, 89.89,







3.85 (d, J = 11.7 Hz,
83.71, 83.58,







1H), 3.55-3.41 (m,
73.08, 72.88,







2H), 2.55 (p, J = 7.0 Hz,
56.13, 51.62,







1H), 2.38 (dt, J = 13.5,
33.85, 33.38,







6.7 Hz, 1H),
29.69, 29.41,







2.21-2.06 (m, 1H),
28.02, 19.80,







1.75 (s, 6H),
19.69, 18.67,







1.73-1.59 (m, 1H),
18.34, 17.98







1.56 (m, 1H), 1.41 (d, J = 6.3 Hz,








3H),








1.41-1.27 (m, 1H), 1.14 (d,








J = 7.0 Hz, 6H),








0.96 (dd, J = 15.0, 7.1 Hz,








1H)



F17
Colorless
—
3378,
HRMS-ESI
1HNMR (CDCl3) δ
13CNMR



Oil

2954
(m/z)
8.59-8.46 (m, 1H),
(CDCl3) δ





2873,
[M + H]+
8.33 (d, J = 5.4 Hz,
172.52,





1772,
calcd for
1H), 7.00 (d, J = 5.5 Hz,
168.91,





1744,
C26H39N2O8,
1H), 4.97 (s, 1H),
162.38,





1679,
507.2705;
4.87 (s, 1H),
159.43,





1508
found,
4.80 (dq, J = 9.2, 6.4 Hz,
146.69,






507.2701
1H), 4.59 (ddd, J = 10.8,
142.52,







8.4, 7.2 Hz,
141.42,







1H), 3.95 (d, J = 12.0 Hz,
137.48,







1H), 3.90 (s, 3H),
112.13,







3.84 (d, J = 12.0 Hz,
109.78, 83.82,







1H), 3.63 (dd, J = 8.6,
83.68, 80.67,







6.1 Hz, 1H),
73.25, 73.12,







3.47-3.32 (m, 3H),
56.29, 51.35,







2.40 (s, 3H),
33.63, 29.12,







2.39-2.30 (m, 1H), 2.11 (dddd,
28.05, 20.76,







J = 15.7, 10.2, 8.1,
19.72, 19.54,







5.1 Hz, 1H), 1.83 (dt,
19.38, 18.30,







J = 13.3, 6.6 Hz, 1H),
17.93







1.76 (t, J = 1.1 Hz,








3H), 1.73-1.59 (m,








2H), 1.39 (d, J = 6.3 Hz,








3H),








1.36-1.26 (m, 1H), 0.95 (dt, J = 7.4,








2.1 Hz, 1H),








0.91 (d, J = 6.7 Hz, 3H),








0.89 (d, J = 6.8 Hz,








3H)



F18
White Solid
73-77
2935,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





1744,
(m/z)
8.53-8.46 (m, 1H),
(CDCl3) δ





1679,
[M + H]+
8.32 (d, J = 5.4 Hz,
172.56,





1508
calcd for
1H), 6.99 (d, J = 5.5 Hz,
169.39,






C28H43N2O9,
1H), 4.77 (dq, J = 9.6,
162.31,






551.2963;
6.4 Hz, 1H),
159.41,






found,
4.58 (ddd, J = 10.7, 8.4,
146.73,






551.2968
7.3 Hz, 1H),
141.44,







4.01 (ddd, J = 8.0, 5.5, 3.4 Hz,
137.31,







1H), 3.89 (s, 3H),
109.77, 83.74,







3.81 (t, J = 6.6 Hz,
81.75, 79.15,







2H), 3.77 (dt, J = 8.8,
75.80, 73.15,







6.6 Hz, 1H), 3.54 (dt,
67.56, 58.77,







J = 8.7, 6.8 Hz, 1H),
56.30, 51.31,







3.44-3.38 (m, 1H),
34.61, 33.68,







3.40 (s, 3H),
33.51, 31.88,







3.30 (dd, J = 9.6, 7.3 Hz,
28.42, 23.64,







1H), 2.98 (t, J = 6.6 Hz,
23.52, 23.33,







2H),
18.49, 17.81,







2.40-2.28 (m, 1H),
10.65







2.14-1.99 (m, 1H),








1.78-1.46 (m, 12H), 1.38 








(d, J = 6.3 Hz, 3H),








1.35-1.26 (m, 1H), 0.92 (t,








J = 7.4 Hz, 3H),








0.90-0.83 (m, 1H)



F19
Off-White
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Foam


(m/z)
12.04 (s, 1H),
(CDCl3) δ






[M + H]+
8.48 (d, J = 8.1 Hz, 1H),
171.93,






calcd for
7.99 (d, J = 5.2 Hz,
168.73,






C28H30N2O7,
1H), 7.30-7.13 (m,
159.50,






506.2053;
4H), 7.11-7.01 (m,
157.55,






found,
2H), 7.01-6.88 (m,
155.38,






506.2053
2H), 6.88-6.79 (m,
148.76,







3H), 5.15 (dq, J = 9.5,
140.57,







6.4 Hz, 1H),
130.32,







4.76-4.60 (m, 2H),
129.46,







4.60-4.45 (m, 1H),
129.45,







3.93 (s, 3H), 2.41 (dt, J = 13.7,
121.68,







7.0 Hz, 1H),
121.59,







2.36-2.18 (m, 1H),
116.90,







1.99-1.84 (m, 1H),
116.54,







1.77 (dt, J = 16.0, 7.8 Hz,
109.54, 82.38,







1H),
82.30, 72.71,







1.46-1.34 (m, 4H), 1.18 (dd, J = 16.1,
56.09, 51.26,







7.8 Hz, 1H)
33.22, 28.18,








18.29, 18.20


F20
White Solid
—
—
HRMS-ESI
1H NMR (CDCl3)
13C NMR






(m/z)
δ 8.33 (d, J = 8.0 Hz,
(CDCl3)






[M + H]+
1H), 8.28 (d, J = 5.4 Hz,
δ 172.54,






calcd for
1H),
170.30,






C31H35N2O9,
7.26-7.16 (m, 5H),
163.02,






579.2337;
7.10-7.02 (m, 2H),
160.29,






found,
6.99-6.88 (m, 3H),
159.53,






578.2234
6.88-6.81 (m, 2H), 5.74 (s, 2H),
157.59,







5.13 (dq, J = 9.5, 6.4 Hz,
145.74,







1H),
144.06,







4.75-4.62 (m, 2H),
142.29,







4.57-4.49 (m, 1H), 3.91 (s, 3H),
129.42,







2.42 (dt, J = 13.6, 7.1 Hz,
121.62,







1H),
121.52,







2.36-2.21 (m, 1H), 2.07 (s, 3H),
116.91,







1.98-1.87 (m, 1H),
116.54,







1.74 (dq, J = 15.5,
109.66, 89.53,







7.8 Hz, 1H), 1.63 (s,
82.44, 82.38,







1H), 1.42 (d, J = 6.4 Hz,
72.44, 56.20,







3H), 1.40-1.28
51.61, 33.29,







(m, 1H), 1.19 (dd, J = 16.1,
28.27, 20.89,







7.7 Hz, 1H)
18.37, 18.19


F21
Hard White
94-95
—
HRMS-ESI
1H NMR (CDCl3)
13C NMR



Foam


(m/z)
δ 12.09 (d, J = 0.4 Hz,
(CDCl3)






[M + Na]+
1H), 8.47 (d, J = 8.2 Hz,
δ 172.05,






calcd for
1H), 7.99 (d,
168.65,






C24H38N2O7Na,
J = 5.2 Hz, 1H),
155.34,






489.2571;
6.86 (d, J = 5.2 Hz, 1H),
148.72,






found,
4.81 (pd, J = 6.3, 2.0 Hz,
140.51,






489.2567
1H), 4.58 (dt, J = 10.8,
130.42,







7.6 Hz, 1H),
109.46, 84.19,







3.94 (s, 3H),
83.70, 80.50,







3.62 (dd, J = 8.6, 6.2 Hz,
75.84, 73.34,







1H), 3.42-3.31 (m,
56.07, 51.31,







3H), 3.28 (dd, J = 8.7,
33.34, 29.09,







6.5 Hz, 1H),
28.90, 27.63,







3.12 (dd, J = 8.7, 6.3 Hz,
19.57, 19.54,







1H), 2.37 (dt, J = 13.8,
19.39, 18.24,







6.5 Hz, 1H),
18.00







2.24-2.06 (m, 1H),








1.82 (dpd, J = 13.2,








6.6, 3.5 Hz, 2H),








1.75-1.58 (m, 2H),








1.45-1.30 (m, 4H),








0.96-0.86 (m, 13H)



F22
Hard White
47-52
3348,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Foam

3029,
(m/z)
12.09 (d, J = 3.1 Hz,
(CDCl3)





2941,
[M + H]+
1H), 8.49 (d, J = 8.0 Hz,
δ 172.03,





2875,
calcd for
1H), 7.97 (d, J = 5.2 Hz,
168.72,





1743,
C30H35N2O7,
1H),
155.35,





1649,
535.2439;
7.42-7.19 (m, 10H),
148.74,





1576,
found,
6.84 (dd, J = 5.1, 1.5 Hz,
140.57,





1528,
535.2433
1H), 4.96-4.80 (m,
138.41,





1497,

2H), 4.69 (d, J = 10.9 Hz,
138.33,





1481,

1H),
130.37,





1450,

4.66-4.53 (m, 2H),
128.43,





1327,

4.53-4.44 (m, 1H), 3.91 (d, J = 2.3 Hz,
128.40,





1242,

3H), 3.66 (d,
127.96,





1216,

J = 7.6 Hz, 2H),
127.83,





1059,

2.38 (dt, J = 13.6, 6.7 Hz,
127.75,





800

1H), 2.30-2.11 (m,
127.69,







1H), 1.88-1.61 (m,
109.54, 83.89,







2H), 1.49-1.32 (m,
83.64, 75.75,







4H), 1.01 (dd, J = 16.1,
73.13, 71.22,







7.3 Hz, 1H)
56.09, 51.33,








33.27, 27.96,








18.35, 18.13


F23
Hard White
58-64
3364,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Foam

2940,
(m/z)
12.06 (s, 1H),
(CDCl3)





1744,
[M + H]+
8.58-8.37 (m, 1H), 7.98 (d,
δ 171.98,





1649,
calcd for
J = 5.2 Hz, 1H),
168.71,





1527,
C29H33N2O7,
7.31-7.19 (m, 5H),
159.50,





1481,
521.2282;
7.14-7.05 (m, 4H),
155.37,





1327,
found,
7.04-6.94 (m, 1H),
148.75,





1240,
521.2274
6.85 (d, J = 5.2 Hz, 1H),
140.57,





1207,

5.04 (dq, J = 9.6, 6.4 Hz,
138.13,





1059,

1H), 4.62 (dt, J = 10.8,
130.34,





1030,

7.6 Hz, 1H),
129.51,





752,

4.57-4.47 (m, 2H),
128.21,





549

4.42 (d, J = 11.5 Hz,
127.82,







1H), 3.92 (s, 3H),
127.56,







3.79-3.69 (m, 1H),
121.45,







2.41 (dt, J = 13.8, 6.6 Hz,
116.34,







1H),
109.54, 82.57,







2.31-2.13 (m, 1H),
82.49, 72.84,







1.98-1.63 (m, 2H),
71.68, 56.09,







1.51-1.30 (m, 4H), 1.09 (dd, J = 16.2,
51.32, 33.31,







7.3 Hz, 1H)
28.16, 18.41,








18.11


F24
Hard White
56-62
3367,
HRMS-ESI
1H NMR (CDCl3)
13C NMR



Foam

3030,
(m/z)
δ 12.06 (s, 1H),
(CDCl3)





2240,
[M + H]+
8.47 (d, J = 8.1 Hz, 1H),
δ 171.95,





1743,
calcd for
8.08-7.89 (m, 1H),
168.71,





1649,
C29H33N2O7,
7.38-7.16 (m, 7H),
157.40,





1596,
521.2282;
7.03-6.91 (m, 3H),
155.37,





1327,
found,
6.85 (d, J = 5.2 Hz,
148.75,





1240,
521.2282
1H), 4.97 (dq, J = 9.6,
140.56,





1211,

6.4 Hz, 1H),
137.91,





1061,

4.84 (d, J = 10.8 Hz, 1H),
130.34,





728,

4.75-4.57 (m, 2H),
129.63,





695

4.50 (t J = 5.4 Hz,
128.36,







1H), 3.93 (s, 3H),
128.23,







3.85 (dd, J = 9.6, 7.2 Hz,
127.82,







1H), 2.37 (dt, J = 13.6,
121.48,







7.0 Hz, 1H),
116.70,







2.29-2.12 (m, 1H),
109.52, 83.13,







1.94-1.78 (m, 1H),
82.91, 75.62,







1.68 (h, J = 8.0 Hz,
72.85, 56.09,







1H), 1.48 (d, J = 6.4 Hz,
51.25, 33.19,







3H),
28.29, 18.23,







1.44-1.29 (m, 1H), 1.09 
18.15







(dd, J = 16.1, 7.8 Hz, 1H)



F25
Off-White
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Foam


(m/z)
12.06 (s, 1H),
(CDCl3) δ






[M + H]+
8.48 (d, J = 8.1 Hz, 1H),
172.00,






calcd for
7.99 (d, J = 5.2 Hz,
168.68,






C26H35N2O7,
1H), 7.31-7.23 (m,
159.66,






487.2437;
2H), 7.08 (d, J = 7.8 Hz,
155.37,






found,
2H), 6.95 (t, J = 7.3 Hz,
148.74,






487.2439
1H), 6.87 (d,
140.54,







J = 5.2 Hz, 1H),
130.37,







5.03 (dq, J = 9.6, 6.4 Hz,
129.33,







1H), 4.62 (dt, J = 10.8,
121.31,







7.7 Hz, 1H),
116.41,







4.44 (dd, J = 9.6, 7.3 Hz,
109.50, 83.06,







1H), 3.94 (s, 3H),
82.76, 76.41,







3.55 (t, J = 5.5 Hz,
72.88, 56.08,







1H), 3.24 (dd, J = 8.7,
51.31, 33.37,







6.6 Hz, 1H),
28.71, 27.88,







3.06 (dd, J = 8.7, 6.2 Hz,
19.36, 19.21,







1H), 2.41 (dt, J = 13.8,
18.29, 18.11







6.6 Hz, 1H),








2.31-2.13 (m, 1H),








1.88-1.60 (m, 3H),








1.51-1.38 (m, 1H),








1.36 (d, J = 6.4 Hz,








3H), 1.04 (dd, J = 16.1,








7.3 Hz, 1H),








0.79 (d, J = 6.7 Hz,








3H), 0.74 (d, J = 6.7 Hz,








3H)



F26
—
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.33 (d, J = 8.0 Hz,
(CDCl3) δ






[M + Na]+
1H), 8.28 (d, J = 5.4 Hz,
172.62,






calcd for
1H),
170.29,






C29H38N2NaO9,
7.32-7.22 (m, 2H),
162.98,






581.2470;
7.13-7.02 (m, 2H),
160.28,






found,
6.99-6.91 (m, 2H), 5.74 (s, 2H),
159.70,






581.2457
5.01 (dq, J = 9.6, 6.4 Hz,
145.73,







1H), 4.64 (dt, J = 10.8,
144.03,







7.6 Hz, 1H),
142.38,







4.43 (dd, J = 9.6, 7.3 Hz,
129.31,







1H), 3.91 (s, 3H),
121.25,







3.54 (t, J = 5.5 Hz,
116.42,







1H), 3.24 (dd, J = 8.8,
109.62 89.54,







6.6 Hz, 1H),
83.14, 82.82,







3.06 (dd, J = 8.8, 6.2 Hz,
76.39, 72.61,







1H), 2.42 (dt, J = 13.7,
56.19, 51.65,







6.7 Hz, 1H)
33.45, 28.70,







2.28-2.12 (m, 1H)
27.95, 20.88,







2.07 (s, 3H),
19.36, 19.21,







1.85-1.56 (m, 3H),
18.36, 18.10







1.45-1.29 (m, 4H),








1.04 (dd, J = 16.1, 7.5 Hz,








1H), 0.79 (d, J = 6.7 Hz,








3H), 0.73 (d, J = 6.7 Hz,








3H)



F27
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
12.06 (d, J = 0.5 Hz,
(CDCl3) δ






[M + H]+
1H), 8.47 (d, J = 8.1 Hz,
171.96,






calcd for
1H), 7.98 (d, J = 5.2 Hz,
168.68,






C26H35N2O7,
1H),
157.54,






487.2439;
7.33-7.20 (m, 2H),
155.35,






found,
7.01-6.89 (m, 3H), 6.86 (d,
148.72,






487.2438
J = 5.2 Hz, 1H),
140.53,







4.93 (dq, J = 9.7, 6.4 Hz,
130.35,







1H), 4.63 (dt, J = 10.8,
129.49,







7.6 Hz, 1H),
121.28,







4.39 (t, J = 5.4 Hz,
116.66,







1H), 3.94 (s, 3H),
109.48, 83.35,







3.64 (dd, J = 9.6, 7.2 Hz,
83.07, 80.68,







1H), 3.57 (dd, J = 8.6,
73.10, 56.07,







6.2 Hz, 1H),
51.24, 33.20,







3.40 (dd, J = 8.6, 6.6 Hz,
28.99, 28.17,







1H), 2.36 (dt, J = 13.6,
19.38, 19.28,







7.0 Hz, 1H),
18.19, 18.01







2.17 (tdd, J = 13.4,








6.4, 4.0 Hz, 1H),








1.89-1.55 (m, 3H),








1.47 (d, J = 6.4 Hz, 3H),








1.35 (q, J = 11.8,








11.4 Hz, 1H),








1.05 (dd, J = 16.1, 7.8 Hz,








1H), 0.83 (d, J = 6.7 Hz,








3H), 0.79 (d, J = 6.7 Hz,








3H)



F28
White
135-137
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Powder


(m/z)
8.31 (d, J = 8.0 Hz,
(CDCl3) δ






[M + H]+
1H), 8.27 (d, J = 5.4 Hz,
172.58,






calcd for
1H),
170.28,






C29H39N2O9,
7.30-7.24 (m, 2H),
162.99,






559.2650;
6.98-6.89 (m, 4H), 5.74 (s, 2H),
160.27,






found,
4.91 (dq, J = 9.7, 6.4 Hz,
157.60,






559.2652
1H), 4.65 (dt, J = 10.7,
145.73,







7.6 Hz, 1H),
144.00,







4.38 (t, J = 5.5 Hz,
142.36,







1H), 3.90 (s, 3H),
129.47,







3.63 (dd, J = 9.6, 7.2 Hz,
121.22,







1H), 3.57 (dd, J = 8.6,
116.68,







6.3 Hz, 1H),
109.62, 89.53,







3.40 (dd, J = 8.6, 6.7 Hz,
83.41, 83.16,







1H), 2.37 (dt, J = 13.6,
80.68, 72.83,







7.0 Hz, 1H),
56.19, 51.58,







2.24-2.09 (m, 1H),
33.30, 29.00,







2.07 (s, 3H),
28.26, 20.88,







1.87-1.56 (m, 3H), 1.46 (d,
19.39, 19.29,







J = 6.4 Hz, 3H),
18.26, 18.00







1.30 (dd, J = 23.8, 10.8 Hz,








1H), 1.04 (dd, J = 16.1,








7.8 Hz, 1H),








0.83 (d, J = 6.7 Hz,








3H), 0.79 (d, J = 6.7 Hz, 3H)



F29
Sticky
—
3378,
HRMS-ESI
1H NMR (CDCl3)
13C NMR



Yellow

2954,
(m/z)
δ 8.32 (d, J = 8.0 Hz,
(CDCl3)



Solid

2872,
[M + H]+
1H), 8.27 (dd, J = 5.3,
δ 172.64,





1745,
calcd for
2.9 Hz, 1H),
170.25,





1676,
C27H43N2O9,
6.95 (d, J = 5.4 Hz, 1H),
162.95,





1577,
539.2963;
5.74 (d, J = 2.6 Hz,
160.24,





1503,
found,
2H), 4.80 (t, J = 6.5 Hz,
145.72,





1463,
539.2957
1H), 4.60 (dt, J = 10.4,
143.94,





1367,

7.8 Hz, 1H),
142.40,





1201,

3.91 (s, 3H),
109.60, 89.50,





1097,

3.62 (dd, J = 8.6, 6.2 Hz,
84.24, 83.71,





1058,

1H), 3.42-3.31 (m,
80.46, 75.78,





1003,

3H), 3.28 (dd, J = 8.6,
73.03, 56.17,





967,

6.5 Hz, 1H),
51.62, 33.38,





912,

3.12 (dd, J = 8.6, 6.3 Hz,
29.06, 28.87,





728

1H), 2.37 (dt, J = 13.6,
27.67, 20.85,







6.7 Hz, 1H),
19.55, 19.52,







2.21-2.09 (m, 1H),
19.37, 18.28,







2.07 (s, 3H),
17.97







1.82 (dtd, J = 13.0, 6.6,








3.6 Hz, 2H),








1.75-1.55 (m, 2H), 1.39 (d,








J = 6.4 Hz, 3H),








1.35-1.21 (m, 1H),








0.97-0.85 (m, 13H)



F30
Fluffy Light
42-52
3376,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Yellow

3030,
(m/z)
8.32 (d, J = 8.0 Hz,
(CDCl3)



Solid

2939,
[M + H]+
1H), 8.27 (d, J = 5.4 Hz,
δ 172.62,





2875,
calcd for
1H),
170.29,





1745,
C33H39N2O9,
7.40-7.23 (m, 10H), 6.94 (d, J = 5.4 Hz,
163.01,





1675,
607.2650;
1H), 5.74 (s,
160.28,





1577,
found,
2H), 4.94-4.80 (m,
145.77,





1497,
607.2648
2H), 4.69 (d, J = 10.9 Hz,
143.99,





1453,

1H),
142.40,





1369,

4.67-4.57 (m, 2H), 4.49 (d, J = 11.4 Hz,
138.44,





1313,

1H), 3.89 (s,
138.37,





1200,

3H), 3.70-3.60 (m,
128.41,





1095,

2H), 2.40 (dt, J = 13.5,
128.38,





1058,

6.8 Hz, 1H),
127.95,





1002,

2.20 (dddd, J = 15.2,
127.82,





965,

12.4, 9.5, 4.4 Hz,
127.71,





828,

1H), 2.07 (s, 3H),
127.65,





736,

1.86-1.62 (m, 2H),
109.66, 89.53,





697

1.43 (d, J = 6.4 Hz,
83.96, 83.72,







3H), 1.40-1.29 (m,
75.75, 72.86,







1H), 1.08-0.95 (m,
71.20, 56.21,







1H)
51.66, 33.37,








28.03, 20.90,








18.41, 18.10


F31
Fluffy
49-55
3380,
HRMS-ESI
1H NMR (CDCl3)
13C NMR



White Solid

2941,
(m/z)
δ 8.33 (d, J = 8.0 Hz,
(CDCl3)





2877,
[M + H]+
1H), 8.27 (d, J = 5.4 Hz,
δ 172.59,





1748,
calcd for
1H),
170.30,





1676,
C32H37N2O9,
7.33-7.18 (m, 5H),
163.01,





1585,
593.2494;
7.14-7.05 (m, 4H),
160.29,





1492,
found,
7.05-6.85 (m, 2H), 5.74 (s, 2H),
159.53,





1368,
593.2499
5.02 (dq, J = 9.6, 6.4 Hz,
145.75,





1200,

1H), 4.64 (dt, J = 10.8,
144.03,





1130,

7.5 Hz, 1H),
142.34,





1030,

4.58-4.47 (m, 2H),
138.17,





1002,

4.47-4.36 (m, 1H),
129.49,





966,

3.90 (s, 3H),
128.19,





829,

3.78-3.66 (m, 1H),
127.81,





752,

2.42 (dt, J = 13.7, 6.7 Hz,
127.52,





694

1H), 2.29-2.13 (m,
121.39,







1H), 2.07 (s, 3H),
116.34,







1.89-1.64 (m, 2H),
109.66, 89.53,







1.44-1.30 (m, 4H),
82.62, 82.56,







1.08 (dd, J = 16.1,
72.57, 71.65,







7.5 Hz, 1H)
56.21, 51.66,








33.39, 28.22,








20.89, 18.47,








18.09


F32
Fluffy
—
3379,
HRMS-ESI
1H NMR (CDCl3)
13C NMR



White Solid

2941,
(m/z)
δ 8.31 (d, J = 8.0 Hz,
(CDCl3)





1747,
[M + H]+
1H), 8.27 (d, J = 5.4 Hz,
δ 172.55,





1676,
calcd for
1H),
170.29,





1584,
C32H37N2O9,
7.37-7.17 (m, 7H), 7.02-6.88
163.01,





1493,
593.2494;
(m, 4H), 5.74 (s, 2H),
160.27,





1454,
found,
4.95 (dq, J = 9.6, 6.3 Hz,
157.45,





1200,
593.2498
1H), 4.85 (d, J = 10.7 Hz,
145.75,





1061,

1H),
144.01,





1002,

4.74-4.61 (m, 2H), 4.49 (t,
142.34,





966,

J = 5.5 Hz, 1H),
137.96,





829,

3.90 (s, 3H), 3.85 (dd, J = 9.6,
129.60,





753,

7.2 Hz, 1H),
128.34,





695

2.38 (dt, J = 13.6, 7.0 Hz,
128.22,







1H), 2.26-2.11 (m,
127.79,







1H), 2.07 (s, 3H),
121.41,







1.91-1.77 (m, 1H),
116.71,







1.66 (dd, J = 16.1,
109.65, 89.52,







7.8 Hz, 1H), 1.47 (d,
83.22, 83.00,







J = 6.4 Hz, 3H),
75.63, 72.58,







1.37-1.23 (m, 1H),
56.20, 51.59,







1.08 (dd, J = 16.1, 7.8 Hz,
33.27, 28.37,







1H)
20.89, 18.30,








18.14


F33
White Solid
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
12.16-12.07 (m,
(CDCl3) δ






[M + Na]+
1H), 8.48 (d, J = 8.1 Hz,
172.10,






calcd for
1H), 7.98 (d, J = 5.2 Hz,
168.64,






C25H38N2NaO7,
1H), 6.86 (d,
155.33,






501.2571;
J = 5.2 Hz, 1H),
148.70,






found,
4.76 (dq, J = 9.7, 6.4 Hz,
140.50,






501.2586
1H), 4.58 (dt, J = 10.8,
130.41,







7.7 Hz, 1H),
109.45, 84.23,







4.31 (d, J = 3.3 Hz,
83.14, 81.18,







1H), 3.94 (s, 3H),
75.92, 73.51,







3.54-3.42 (m, 1H),
56.06, 51.33,







3.32 (t, J = 5.6 Hz,
33.31, 32.94,







1H), 3.24 (dd, J = 8.6,
32.31, 28.90,







7.0 Hz, 1H),
27.59, 23.26,







3.15 (dd, J = 8.6, 6.0 Hz,
23.19, 19.63,







1H), 2.36 (dt, J = 13.7,
19.48, 18.27,







6.6 Hz, 1H),
18.13







2.25-2.08 (m, 1H),








1.90-1.50 (m, 11H),








1.44-1.30 (m, 4H),








0.92 (dd, J = 6.7, 4.8 Hz,








7H)



F34
Clear Tacky
—
—
HRMS-ESI
1H NMR (CDCl3)
13C NMR



Solid


(m/z)
δ 8.39 (d, J = 8.0 Hz,
(CDCl3)






[M + H]+
1H), 8.27 (d, J = 5.4 Hz,
δ 176.25,






calcd for
1H),
172.60,






C31H43N2O9,
7.34-7.22 (m, 2H), 7.08 (d, J = 8.0 Hz,
162.96,






587.2963;
2H), 6.95 (t, J = 6.5 Hz,
160.25,






found,
2H),
159.70,






587.3065
5.84-5.71 (m, 2H),
145.59,







5.01 (dq, J = 9.6, 6.4 Hz,
144.23,







1H), 4.64 (dt, J = 10.7,
142.03,







7.6 Hz, 1H),
129.31,







4.43 (dd, J = 9.6, 7.3 Hz,
121.25,







1H), 3.89 (s, 3H),
116.42,







3.54 (t, J = 5.6 Hz,
109.57, 89.88,







1H), 3.24 (dd, J = 8.7,
83.14, 82.82,







6.6 Hz, 1H),
76.38, 72.59,







3.06 (dd, J = 8.7, 6.3 Hz,
56.14, 51.65,







1H), 2.55 (p, J = 7.0 Hz,
33.85, 33.44,







1H), 2.42 (dt, J = 13.6,
28.70, 27.94,







6.7 Hz, 1H)
19.36, 19.21,







2.20 (dp, J = 15.7,
18.68, 18.36,







5.1 Hz, 1H),
18.09







1.86-1.61 (m, 3H),








1.45-1.31 (m, 4H), 1.14 (d,








J = 7.0 Hz, 6H),








1.04 (dd, J = 16.1, 7.5 Hz,








1H), 0.79 (d, J = 6.7 Hz,








3H), 0.73 (d, J = 6.7 Hz,








3H)



F35
Clear Tacky
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Solid


(m/z)
8.37 (d, J = 8.1 Hz,
(CDCl3) δ






[M + H]+
1H), 8.26 (d, J = 5.4 Hz,
176.25,






calcd for
1H),
172.57,






C31H43N2O9,
7.35-7.22 (m, 2H),
162.97,






587.2963;
7.01-6.87 (m, 4H),
160.25,






found,
5.83-5.67 (m, 2H), 4.91 (dq, J = 9.7,
157.60,






587.2952
6.4 Hz, 1H),
145.59,







4.65 (dt, J = 10.7, 7.6 Hz,
144.22,







1H), 4.38 (t, J = 5.4 Hz,
142.02,







1H), 3.88 (s, 3H),
129.47,







3.63 (dd, J = 9.6, 7.2 Hz,
121.22,







1H), 3.57 (dd, J = 8.7,
116.67,







6.3 Hz, 1H),
109.55, 89.90,







3.40 (dd, J = 8.7, 6.7 Hz,
83.41, 83.16,







1H), 2.55 (p, J = 7.0 Hz,
80.68, 72.81,







1H), 2.36 (dt, J = 13.6,
56.13, 51.57,







7.0 Hz, 1H),
33.86, 33.31,







2.23-2.08 (m, 1H),
28.99, 28.25,







1.90-1.56 (m, 3H),
19.39, 19.29,







1.46 (d, J = 6.4 Hz,
18.68, 18.27,







3H), 1.36-1.27 (m,
18.00







1H), 1.14 (d, J = 7.0 Hz,








6H), 1.05 (dd, J = 16.1,








7.9 Hz, 1H),








0.83 (d, J = 6.7 Hz,








3H), 0.79 (d, J = 6.7 Hz,








3H)



F36
Clear Tacky
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Solid


(m/z)
8.39 (d, J = 8.0 Hz,
(CDCl3) δ






[M + Na]+
1H), 8.27 (d, J = 5.4 Hz,
176.26,






calcd for
1H),
172.53,






C33H38N2NaO9,
7.29-7.15 (m, 4H),
162.99,






629.2470;
7.10-7.03 (m, 2H),
160.26,






found,
6.98-6.88 (m, 3H),
159.53,






629.2460
6.88-6.82 (m, 2H),
157.59,







5.81-5.74 (m, 2H), 5.13 (dq, J = 9.6,
145.60,







6.4 Hz, 1H),
144.26,







4.67 (ddd, J = 9.6, 7.6, 3.1 Hz,
141.95,







2H),
129.43,







4.56-4.51 (m, 1H), 3.88 (s, 3H),
129.41, 121.61,







2.55 (p, J = 7.0 Hz,
121.52,







1H), 2.42 (dt, J = 13.6,
116.90,







7.1 Hz, 1H),
116.54,







2.35-2.21 (m, 1H),
109.60, 89.87,







1.98-1.85 (m, 1H),
82.45, 82.38,







1.74 (dt, J = 24.4, 8.1 Hz,
72.42, 56.15,







1H), 1.42 (d, J = 6.4 Hz,
51.60, 33.86,







3H), 1.36 (d,
33.29, 28.26,







J = 13.1 Hz, 1H),
18.69, 18.37,







1.22-1.17 (m, 1H),
18.18







1.14 (d, J = 7.0 Hz,








6H)



F37
Clear Tacky
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Solid


(m/z)
8.37 (d, J = 8.1 Hz,
(CDCl3) δ






[M + Na]+
1H), 8.27 (d, J = 5.3 Hz,
176.24,






calcd for
1H), 6.94 (d, J = 5.4 Hz,
172.65,






C29H46N2NaO9,
1H),
162.93,






589.3096;
5.83-5.72 (m, 2H),
160.24,






found,
4.79 (dq, J = 12.6, 6.2 Hz,
145.58,






589.3090
1H), 4.60 (dt, J = 10.7,
144.19,







7.6 Hz, 1H),
142.10,







3.89 (s, 3H),
109.52, 89.91,







3.62 (dd, J = 8.6, 6.2 Hz,
84.26, 83.74,







1H), 3.41-3.31 (m,
80.49, 75.81,







3H), 3.28 (dd, J = 8.6,
73.04, 56.12,







6.5 Hz, 1H),
51.63, 33.85,







3.12 (dd, J = 8.6, 6.3 Hz,
33.43, 29.08,







1H), 2.55 (p, J = 7.0 Hz,
28.88, 27.69,







1H), 2.37 (dt, J = 13.5,
19.57, 19.54,







6.7 Hz, 1H),
19.53, 19.39,







2.12 (ddt, J = 10.7,
18.67, 18.29,







8.2, 5.6 Hz, 1H),
17.98







1.90-1.54 (m, 4H),








1.39 (d, J = 6.4 Hz, 3H),








1.38-1.27 (m, 1H),








1.14 (d, J = 7.0 Hz,








6H), 0.90 (t, J = 7.0 Hz,








13H)



F38
Clear Tacky
—
—
HRMS-ESI
1NMR (CDCl3) δ
13C NMR



Solid


(m/z)
8.37 (d, J = 8.1 Hz,
(CDCl3) δ






[M + Na]+
1H), 8.27 (d, J = 5.4 Hz,
176.23,






calcd for
1H), 6.94 (d, J = 5.4 Hz,
172.71,






C30H46N2NaO9,
1H),
162.92,






601.3096;
5.83-5.72 (m, 2H),
160.23,






found,
4.74 (dq, J = 9.6, 6.4 Hz,
145.58,






601.3105
1H), 4.60 (dt, J = 10.8,
144.18,







7.6 Hz, 1H),
142.12,







4.38-4.27 (m, 1H),
109.51, 89.90,







3.89 (s, 3H),
84.31, 83.13,







3.46 (dd, J = 9.6, 7.0 Hz,
81.25, 75.91,







1H), 3.31 (t, J = 5.5 Hz,
73.22, 56.12,







1H), 3.24 (dd, J = 8.6,
51.65, 33.85,







7.0 Hz, 1H),
33.42, 32.95,







3.14 (dd, J = 8.7, 6.0 Hz,
32.31, 28.89,







1H), 2.55 (hept, J = 7.0 Hz,
27.68, 23.26,







1H), 2.37 (dt,
23.18, 19.63,







J = 13.6, 6.7 Hz, 1H),
19.49, 18.67,







2.17-2.06 (m, 1H),
18.34, 18.13







1.90-1.47 (m, 11H),








1.38 (d, J = 6.4 Hz,








3H), 1.32 (d, J = 11.3 Hz,








1H), 1.14 (d, J = 7.0 Hz,








6H), 0.92 (d,








J = 4.5 Hz, 3H),








0.91 (d, J = 4.6 Hz, 3H),








0.88 (d, J = 7.5 Hz,








1H)



F39
Clear Tacky
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Solid


(m/z)
8.32 (d, J = 8.1 Hz,
(CDCl3) δ






[M + H]+
1H), 8.27 (d, J = 5.4 Hz,
172.73,






calcd for
1H), 6.94 (d, J = 5.4 Hz,
170.27,






C28H43N2O9,
1H), 5.74 (s,
162.95,






551.2963;
2H), 4.74 (dq, J = 9.6,
160.26,






found,
6.4 Hz, 1H),
145.72,






551.2962
4.60 (dt, J = 10.8, 7.5 Hz,
143.97,







1H), 4.31 (p, J = 5.3,
142.46,







4.6 Hz, 1H), 3.91 (s,
109.57, 89.55,







3H), 3.46 (dd, J = 9.6,
84.31, 83.13,







7.0 Hz, 1H),
81.25, 75.91,







3.31 (t, J = 5.5 Hz, 1H),
73.24, 56.18,







3.24 (dd, J = 8.6, 6.9 Hz,
51.66, 33.42,







1H), 3.14 (dd, J = 8.7,
32.95, 32.31,







6.0 Hz, 1H),
28.89, 27.68,







2.37 (dt, J = 13.6, 6.7 Hz,
23.26, 23.19,







1H), 2.07 (s, 4H),
20.87, 19.64,







1.89-1.46 (m, 11H),
19.49, 18.34,







1.38 (d, J = 6.4 Hz,
18.13







3H), 1.32 (d, J = 11.3 Hz,








1H), 0.92 (dd, J = 6.7,








4.6 Hz, 7H)



F40
colorless
—
3367,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



semi solid

2949,
(m/z)
12.09 (s, 1H),
(CDCl3) δ





2870,
[M + Na]+
8.47 (d, J = 8.2 Hz, 1H),
172.04,





1742,
calcd for
7.99 (d, J = 5.2 Hz,
168.62,





1650,
C29H40N2NaO7,
1H), 7.33-7.23 (m,
155.38,





1528
551.2728;
2H), 7.23-7.13 (m,
148.73,






found,
3H), 6.87 (d, J = 5.3 Hz,
142.02,






551.2734
1H),
140.49,







4.86-4.77 (m, 1H), 4.58 (dt, J = 10.8,
130.36,







7.6 Hz, 1H),
128.35,







3.94 (s, 3H), 3.85 (dt,
128.32,







J = 9.1, 6.4 Hz, 1H),
125.77,







3.64 (dt, J = 9.1, 6.5 Hz,
109.45, 84.16,







1H),
83.85, 75.83,







3.43-3.32 (m, 2H), 3.27 (dd, J = 8.7,
73.19, 73.00,







6.6 Hz, 1H),
56.08, 51.31,







3.10 (dd, J = 8.7, 6.2 Hz,
33.31, 32.51,







1H), 2.68 (td, J = 7.6,
32.00, 28.86,







3.9 Hz, 2H),
27.62, 19.54,







2.43-2.30 (m, 1H),
19.48, 18.21,







2.21-2.08 (m, 1H),
18.02







1.96-1.84 (m, 2H),








1.78 (dq, J = 13.1, 6.5 Hz,








1H), 1.72-1.62 (m,








2H), 1.43-1.33 (m,








4H), 0.95-0.90 (m,








1H), 0.89 (dd, J = 6.7,








3.0 Hz, 6H)



F41
White Solid
108-114
3370,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2955,
(m/z)
12.07 (s, 1H),
(CDCl3) δ





2874,
[M + Na]+
8.47 (d, J = 8.2 Hz, 1H),
171.99,





1744,
calcd for
7.99 (d, J = 5.2 Hz,
168.60,





1651,
C24H35F3N2NaO7,
1H), 6.87 (d, J = 5.2 Hz,
155.45,





1530,
543.2289;
1H), 4.80 (dq, J = 9.1,
148.77,





1263
found,
6.3 Hz, 1H),
140.45, δ






543.2291
4.58 (dt, J = 10.7, 7.6 Hz,
133.17-125.57 (m),







1H), 3.94 (s, 3H),
109.46, 83.99,







3.86 (dt, J = 9.2, 6.1 Hz,
83.96, 75.65,







1H), 3.68 (dt, J = 9.2,
72.93, 71.69,







6.3 Hz, 1H),
56.10, 51.31,







3.43-3.31 (m, 2H),
33.25,







3.28 (dd, J = 8.7, 6.7 Hz,
30.90 (q, J = 28.9 Hz),







1H), 3.09 (dd, J = 8.6,
28.88,







6.1 Hz, 1H),
27.39,







2.44-2.29 (m, 1H),
23.07 (q, J = 2.4 Hz),







2.26-2.09 (m, 3H),
19.54,







1.86-1.75 (m, 3H),
19.46, 18.16,







1.71-1.58 (m, 3H),
17.96







1.39 (d, J = 6.4 Hz, 3H),








0.97-0.85 (m, 7H)



F42
White Solid
167-169
3387,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2955,
(m/z)
8.50 (d, J = 8.3 Hz,
(CDCl3) δ





2877,
[M + H]+
1H), 8.33 (d, J = 5.5 Hz,
173.90,





1772,
calcd for
1H), 7.00 (d, J = 5.4 Hz,
172.61,





1735,
C26H37N2O9,
1H), 5.13 (dd,
168.93,





1679,
521.2494;
J = 9.8, 7.8 Hz, 1H),
162.36,





1508,
found,
4.95 (dq, J = 9.8, 6.4 Hz,
159.45,





1168
521.2505
1H), 4.63 (dt, J = 10.6,
146.66,







7.7 Hz, 1H),
141.39,







3.91 (s, 3H),
137.52,







3.37 (ddd, J = 7.6, 5.3, 1.9 Hz,
109.80, 81.19,







1H), 3.30 (dd, J = 8.8,
76.33, 75.64,







6.1 Hz, 1H),
71.49, 56.29,







2.98 (dd, J = 8.8, 6.8 Hz,
51.33, 33.64,







1H), 2.40 (s, 3H),
28.63, 28.12,







2.43-2.33 (m, 1H),
20.76, 19.32,







2.22-2.02 (m, 1H),
19.26, 18.03,







1.84-1.56 (m, 4H),
17.20, 12.88,







1.40-1.29 (m, 1H),
8.45, 8.38







1.28 (d, J = 6.4 Hz,








3H), 1.07-0.95 (m,








3H), 0.91-0.81 (m,








8H)



F43
Colorless
—
3389,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Semi-Solid

2950,
(m/z)
8.31 (d, J = 8.0 Hz,
(CDCl3) δ





2870,
[M + H]+
1H), 8.28 (d, J = 5.3 Hz,
172.68,





1750,
calcd for
1H),
170.31,





1678,
C32H45N2O9,
7.31-7.23 (m, 2H),
162.97,





1503,
601.3120;
7.22-7.14 (m, 3H), 6.94 (d, J = 5.4 Hz,
160.27,





1202
found,
1H), 5.74 (s,
145.73,






601.3136
2H), 4.84-4.75 (m,
144.00,







1H), 4.60 (dt, J = 10.7,
142.44,







7.6 Hz, 1H),
142.06,







3.91 (s, 3H), 3.85 (dt,
128.36,







J = 9.1, 6.4 Hz, 1H),
128.33,







3.64 (dt, J = 9.2, 6.5 Hz,
125.77,







1H),
109.58, 99.98,







3.41-3.31 (m, 2H), 3.27 (dd, J = 8.8,
89.57, 84.25,







6.6 Hz, 1H),
83.91, 75.82,







3.09 (dd, J = 8.7, 6.3 Hz,
73.01, 72.93,







1H), 2.75-2.62 (m,
56.18, 51.63,







2H), 2.37 (dt, J = 13.5,
33.43, 32.52,







6.9 Hz, 1H),
32.02, 28.86,







2.17-2.07 (m, 1H),
27.70, 20.89,







2.07 (s, 3H),
19.54, 19.49,







1.94-1.83 (m, 2H),
18.28, 18.01







1.78 (dt, J = 13.2, 6.7 Hz,








1H), 1.70-1.58 (m,








2H), 1.40 (d, J = 6.3 Hz,








3H), 1.32 (q, J = 11.0 Hz,








1H),








0.95-0.89 (m, 1H),








0.89 (dd, J = 6.7, 2.9 Hz,








6H)



F44
Colorless
—
3382,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Semi-Solid

2954,
(m/z)
8.31 (d, J = 8.1 Hz,
(CDCl3) δ





2875,
[M + H]+
1H), 8.28 (d, J = 5.4 Hz,
172.63,





1750,
calcd for
1H), 6.95 (d, J = 5.4 Hz,
170.31,





1678,
C27H40F3N2O9,
1H), 5.74 (s,
162.98,





1504,
593.2680;
2H), 4.78 (dq, J = 9.3,
160.27,





1203
found,
6.4 Hz, 1H),
145.73,






593.2697
4.60 (dt, J = 10.8, 7.6 Hz,
144.01,







1H), 3.91 (s, 3H),
142.39,







3.85 (dt, J = 9.3, 6.1 Hz,
109.60, 89.55,







1H), 3.67 (dt, J = 9.3,
84.07, 84.01,







6.1 Hz, 1H),
75.63, 72.67,







3.42-3.30 (m, 2H),
71.68, 56.19,







3.27 (dd, J = 8.7, 6.6 Hz,
51.61,







1H), 3.09 (dd, J = 8.6,
30.91 (q, J = 29.1 Hz),







6.1 Hz, 1H),
28.87,







2.47-2.32 (m, 1H),
27.47, 23.09,







2.28-2.09 (m, 3H),
23.06, 20.89,







2.07 (s, 3H),
19.54, 19.46,







1.87-1.77 (m, 3H),
18.22, 17.95;







1.71-1.61 (m, 2H), 1.38 (d, J = 6.3 Hz,
19F NMR







3H),
(CDCl3) δ







1.37-1.23 (m, 1H),
−66.38-−66.51 (m)







0.91 (dd, J = 6.8, 1.8 Hz,








6H), 0.89-0.85 (m,








1H)



F45
Colorless
—
3376,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Semi-Solid

2956,
(m/z)
8.32 (d, J = 8.0 Hz,
(CDCl3) δ





2873,
[M + Na]+
1H), 8.27 (dd, J = 5.5,
172.63,





1745,
calcd for
1.5 Hz, 1H),
170.24,





1676,
C26H40N2NaO9,
6.95 (d, J = 5.4 Hz, 1H),
162.95,





1502,
547.2626;
5.75-5.72 (m, 2H),
160.24,





1236
found,
4.78 (p, J = 6.8 Hz,
145.72,






547.2624
1H), 4.60 (dt, J = 11.0,
143.93,







7.6 Hz, 1H),
142.41,







3.91 (s, 3H), 3.78 (dt,
109.60, 89.49,







J = 9.4, 6.6 Hz, 1H),
84.22, 83.76,







3.62-3.52 (m, 1H),
75.90, 75.39,







3.41-3.32 (m, 2H),
72.99, 56.17,







3.29 (dd, J = 8.7, 6.5 Hz,
51.62, 33.40,







1H),
28.85, 27.75,







3.16-3.10 (m, 1H), 2.37 (dt, J = 13.5,
23.50, 20.85,







6.8 Hz, 1H),
19.50, 19.47,







2.18-2.09 (m, 1H),
18.27, 17.88,







2.07 (s, 3H),
10.67







1.82 (hept, J = 6.6 Hz,








1H), 1.71-1.53 (m,








4H), 1.40 (d, J = 6.5 Hz,








3H),








1.38-1.22 (m, 1H),








0.97-0.85 (m, 10H)



F46
Colorless
—
3378,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Semi-Solid

2954,
(m/z)
8.37-8.23 (m, 2H),
(CDCl3) δ





2873,
[M + Na]+
6.95 (d, J = 5.4 Hz,
173.90,





1732,
calcd for
1H), 5.74 (s, 2H),
172.72,





1676,
C27H38N2NaO10,
5.15 (dd, J = 9.8, 7.8 Hz,
170.32,





1501,
573.2419;
1H), 4.96 (dq, J = 9.6,
162.96,





1163
found,
6.4 Hz, 1H),
160.29,






573.2415
4.63 (dt, J = 10.7, 7.5 Hz,
145.69,







1H), 3.91 (s, 3H),
144.10,







3.38 (ddt, J = 7.6,
142.34,







5.4, 3.0 Hz, 1H),
109.61, 89.58,







3.30 (dd, J = 8.8, 6.1 Hz,
76.33, 75.67,







1H), 2.98 (dd, J = 8.8,
71.49, 56.19,







6.8 Hz, 1H),
51.64, 33.41,







2.40 (dt, J = 13.8, 7.3 Hz,
28.65, 28.13,







1H), 2.15 (dddd, J = 15.8,
20.88, 19.32,







10.1, 8.0, 5.4 Hz,
19.27, 18.08,







1H), 2.07 (s, 3H),
17.23, 12.89,







1.77 (dt, J = 13.3, 6.7 Hz,
8.44, 8.37







2H),








1.72-1.56 (m, 2H),








1.43-1.32 (m, 1H), 1.29 (d, J = 6.4 Hz,








3H),








1.08-0.99 (m, 3H),








0.90-0.84 (m, 8H)



F47
Yellow-
—
3375,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Semi Solid

2956,
(m/z)
8.56-8.48 (m, 1H),
(CDCl3) δ





2874,
[M + H]+
8.33 (d, J = 5.4 Hz,
172.55,





1772,
calcd for
1H), 7.00 (d, J = 5.5 Hz,
168.92,





1744,
C25H39N2O8,
1H), 4.78 (t, J = 7.7 Hz,
162.38,





1679,
495.2701;
1H), 4.59 (dt,
159.42,





1508,
found,
J = 10.7, 7.7 Hz, 1H),
146.69,





1198
495.2713
3.91 (s, 3H), 3.77 (dt,
141.43,







J = 8.8, 6.5 Hz, 1H),
137.47,







3.56 (dt, J = 8.9, 6.8 Hz,
109.77, 84.25,







1H),
83.77, 75.95,







3.42-3.31 (m, 2H), 3.28 (dd, J = 8.8,
75.44, 73.04,







6.4 Hz, 1H),
56.28, 51.35,







3.12 (dd, J = 8.8, 6.3 Hz,
28.86, 27.77,







1H), 2.40 (s, 3H),
23.52, 20.76,







2.38-2.26 (m, 1H),
19.52, 19.49,







2.17-2.05 (m, 1H),
18.23, 17.87,







1.81 (dt, J = 13.2, 6.6 Hz,
10.68







1H),








1.72-1.56 (m, 3H), 1.38 (d, J = 6.4 Hz,








3H),








1.36-1.19 (m, 2H),








1.02-0.81 (m, 10H)



F48
White Solid
—
—
ESIMS
1H NMR (CDCl3) δ
19F NMR






m/z 616.2
8.33 (d, J = 7.9 Hz,
(CDCl3) δ−122.28,






([M + H]+)
1H), 8.28 (d, J = 5.4 Hz,
−122.60







1H),








7.03-6.87 (m, 7H),








6.82-6.75 (m, 2H), 5.74 (s, 2H),








5.10 (dq, J = 9.7, 6.4 Hz,








1H), 4.68 (dt, J = 10.7,








7.5 Hz, 1H),








4.53 (dd, J = 9.6, 7.4 Hz,








1H), 4.40 (ddd, J = 7.3,








5.2, 1.8 Hz,








1H), 3.91 (s, 3H),








2.43 (dt, J = 13.8, 7.0 Hz,








1H),








2.29-2.16 (m, 1H),








2.07 (s, 3H),








1.95-1.81 (m, 1H),








1.81-1.68 (m, 1H),








1.42 (d, J = 6.4 Hz,








3H), 1.41-1.28 (m,








1H), 1.23-1.10 (m,








1H)



F49
White Solid
—
—
ESIM
1H NMR (CDCl3) δ
19F NMR






m/z 643.2
8.38 (d, J = 8.0 Hz,
(CDCl3) δ−122.29,






([M + H]+)
1H), 8.27 (d, J = 5.3 Hz,
−122.61







1H),








7.03-6.86 (m, 7H),








6.82-6.76 (m, 2H),








5.80-5.74 (m, 2H), 5.10 (dq, J = 9.5,








6.3 Hz, 1H),








4.68 (dt, J = 10.8, 7.6 Hz,








1H), 4.53 (dd, J = 9.6,








7.3 Hz, 1H),








4.40 (ddd, J = 7.3, 5.2, 1.8 Hz,








1H), 3.89 (s, 3H),








2.55 (p, J = 7.0 Hz,








1H), 2.42 (dt, J = 13.9,








7.1 Hz, 1H),








2.22 (dddd, J = 15.8,








10.3, 7.9, 5.2 Hz,








1H), 1.94-1.82 (m,








1H), 1.80-1.67 (m,








1H), 1.42 (d, J = 6.4 Hz,








3H),








1.40-1.33 (m, 1H),








1.33-1.26 (m, 1H), 1.14 (d, J = 7.0 Hz,








6H)



F50
White Solid
89-91
3364,
HRMS ESI
1H NMR (CDCl3) δ
13C NMR





2918,
(m/z)
12.04 (s, 1H),
(CDCl3) δ





1745,
calcd for
8.49 (d, J = 8.1 Hz, 1H),
171.92,





1649,
C28H28F2N2O7,
7.98 (d, J = 5.2 Hz,
168.81,





1502,
542.1865;
1H), 7.05-6.75 (m,
157.81 (d, J = 239.9 Hz),





1200
found,
9H), 5.11 (dq, J = 9.6,
155.66 (d, J = 2.0 Hz),






542.1872
6.3 Hz, 1H),
155.44,







4.67 (dt, J = 10.8, 7.6 Hz,
154.63 (d, J = 208.1 Hz),







1H), 4.54 (dd, J = 9.5,
153.60 (d, J = 2.0 Hz),







7.4 Hz, 1H),
148.82,







4.41 (ddd, J = 7.1, 5.2, 1.8 Hz,
140.65,







1H), 3.93 (s, 3H),
130.31,







2.42 (dt, J = 13.7, 7.2 Hz,
118.35 (d, J = 8.0 Hz),







1H),
117.77 (d, J = 8.2 Hz),







2.31-2.16 (m, 1H),
116.05 (d, J = 6.3 Hz),







1.96-1.82 (m, 1H),
115.82 (d, J = 6.6 Hz),







1.85-1.68 (m, 1H),
109.63, 83.67,







1.47-1.36 (m, 1H), 1.43 (d, J = 6.3 Hz,
83.43, 72.51,







3H),
56.14, 51.27,







1.16 (ddt, J = 15.9, 7.6,
33.22, 28.20,







1.8 Hz, 1H)
18.33, 18.23


F51
Colorless
—
3376,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Oil

2954,
(m/z)
8.37 (d, J = 8.0 Hz,
(CDCl3) δ





2875,
[M + H]+
1H), 8.27 (d, J = 5.3 Hz,
176.27,





1746,
calcd for
1H), 6.94 (d, J = 5.4 Hz,
172.62,





1679,
C29H44F3N2O9,
1H),
162.95,





1504,
621.2993;
5.85-5.67 (m, 2H),
160.26,





1253,
found,
4.78 (dq, J = 9.2, 6.3 Hz,
145.60,





1100,
621.3003
1H), 4.60 (dt, J = 10.8,
144.23,





833

7.6 Hz, 1H),
142.05,







3.89 (s, 3H),
109.54, 89.92,







3.87-3.81 (m, 1H),
84.08, 84.02,







3.68 (dt, J = 9.2, 6.3 Hz,
75.63, 72.65,







1H), 3.41-3.31 (m,
71.69, 56.14,







2H), 3.28 (dd, J = 8.7,
51.61, 33.86,







6.6 Hz, 1H),
33.39,







3.09 (dd, J = 8.7, 6.2 Hz,
30.91 (q, J = 28.7 Hz),







1H), 2.55 (hept, J = 7.0 Hz,
28.88,







1H),
27.47,







2.37 (dtd, J = 13.6, 6.6,
23.08 (q, J = 2.4 Hz),







1.7 Hz, 1H),
19.55,







2.26-2.06 (m, 3H),
19.47, 18.69,







1.86-1.76 (m, 3H),
18.23, 17.95;







1.75-1.56 (m, 2H), 1.38 (d,
19F NMR







J = 6.3 Hz, 3H),
(CDCl3) δ







1.35-1.25 (m, 1H),
−66.43 (t, J = 11.0 Hz)







1.14 (d, J = 7.0 Hz, 6H),








0.91 (dd, J = 6.7, 1.8 Hz,








6H),








0.93-0.86 (m, 1H)



F52
Colorless
—
3379,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Oil

2955,
(m/z)
8.36 (d, J = 7.9 Hz,
(CDCl3) δ





2874,
[M + H]+
1H), 8.27 (d, J = 5.3 Hz,
176.29,





1736,
calcd for
1H), 6.95 (d, J = 5.3 Hz,
173.90,





1678,
C29H43N2O10,
1H),
172.72,





1503,
579.2912;
5.81-5.72 (m, 2H),
162.92,





1383,
found,
5.15 (dd, J = 9.8, 7.8 Hz,
160.26,





1315,
579.2922
1H), 4.96 (dq, J = 9.7,
145.55,





1165,

6.4 Hz, 1H),
144.31,





1094,

4.63 (dt, J = 10.6, 7.5 Hz,
141.99,





1027,

1H), 3.89 (s, 3H),
109.53, 89.94,





973

3.38 (ddd, J = 7.6,
81.20, 76.32,







5.4, 1.9 Hz, 1H),
75.66, 71.46,







3.31 (dd, J = 8.8, 6.1 Hz,
56.13, 51.63,







1H), 2.99 (dd, J = 8.8,
33.86, 33.40,







6.8 Hz, 1H),
28.64, 28.11,







2.55 (hept, J = 7.0 Hz,
19.32, 19.27,







1H), 2.44-2.29 (m,
18.69, 18.07,







1H), 2.23-2.05 (m,
17.22, 12.88,







1H), 1.84-1.56 (m,
8.45, 8.38







4H), 1.44-1.29 (m,








1H), 1.29 (d, J = 6.4 Hz,








3H), 1.14 (d, J = 7.0 Hz,








6H),








1.07-0.98 (m, 3H),








0.92-0.83 (m, 8H)



F53
Colorless
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Semi-Solid


(m/z)
12.07 (s, 1H),
(CDCl3) δ






[M + H]+
8.48 (d, J = 8.2 Hz, 1H),
171.97,






calcd for
7.98 (d, J = 5.2 Hz,
168.68,






C24H34F3N2O7,
1H), 6.87 (d, J = 5.2 Hz,
155.36,






519.2313;
1H), 6.43 (dtt, J = 13.6,
148.73,






found,
4.0, 2.0 Hz,
140.55,






519.2324
1H), 5.90 (dqt, J = 15.3,
136.86 (q, J = 6.3 Hz),







6.6, 2.2 Hz,
130.35,







1H), 4.86 (dq, J = 9.4,
123.14 (q, J = 269.1 Hz),







6.3 Hz, 1H),
118.09 (q, J = 34.1 Hz),







4.60 (dt, J = 10.7, 7.6 Hz,
109.50, 84.27,







1H), 4.54-4.45 (m,
83.94, 75.68,







1H), 4.34-4.25 (m,
72.65, 71.03,







1H), 3.94 (s, 3H),
56.08, 51.26,







3.46 (dd, J = 9.4, 7.2 Hz,
33.26, 28.84,







1H),
27.44, 19.49,







3.44-3.36 (m, 1H), 3.28 (dd, J = 8.7,
19.40, 18.16,







6.6 Hz, 1H),
17.96;







3.09 (dd, J = 8.7, 6.1 Hz,
19F NMR







1H), 2.44-2.31 (m,
(CDCl3) δ −64.24







1H), 2.24-2.09 (m,








1H), 1.88-1.75 (m,








1H), 1.75-1.59 (m,








2H), 1.41 (d, J = 6.3 Hz,








3H),








1.40-1.30 (m, 1H),








0.98-0.93 (m, 1H), 0.90 (dd, J = 6.7,








3.3 Hz, 6H)



F54
Colorless
—
3369,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Oil

2946,
(m/z)
12.03 (s, 1H),
(CDCl3) δ





1747,
[M]+
8.47 (d, J = 8.1 Hz, 1H),
172.01,





1651,
calcd for
7.99 (d, J = 5.2 Hz,
168.85,





1504,
C29H31FN2O8,
1H), 7.07-7.01 (m,
157.85 (d, J = 239.3 Hz),





1203
554.2064;
2H), 6.98-6.90 (m,
155.90 (d, J = 2.2 Hz),






found,
2H), 6.87 (d, J = 5.2 Hz,
155.52,






554.2074
1H),
154.80,







6.84-6.74 (m, 4H), 5.11 (dq, J = 9.6,
151.52,







6.4 Hz, 1H),
148.89,







4.66 (dt, J = 10.8, 7.7 Hz,
140.70,







1H), 4.53 (dd, J = 9.6,
130.44,







7.4 Hz, 1H),
118.68,







4.36 (ddd, J = 7.2, 5.2, 1.8 Hz,
117.96 (d, J = 7.9 Hz),







1H), 3.94 (s, 3H),
115.95 (d, J = 23.0 Hz),







3.74 (s, 3H), 2.42 (dt,
114.74,







J = 13.8, 7.3 Hz, 1H),
109.67, 84.07,







2.24 (dddd, J = 15.8,
83.69, 72.67,







10.3, 8.0, 5.1 Hz,
56.23, 55.78,







1H), 1.96-1.84 (m,
51.36, 33.39,







1H), 1.84-1.72 (m,
28.18, 18.44,







1H), 1.44-1.34 (m,
18.35;







1H), 1.43 (d, J = 6.4 Hz,
19F NMR







3H), 1.12 (ddt, J = 16.2,
(CDCl3) δ −122.66







7.8, 1.8 Hz,








1H)



F55
Colorless
65-67
2953,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Solid

2873,
(m/z)
12.06 (s, 1H),
(CDCl3) δ





1746,
[M]+
8.48 (d, J = 8.1 Hz, 1H),
171.95,





1651,
calcd for
7.99 (d, J = 5.1 Hz,
168.69,





1503,
C26H33FN2O7,
1H), 7.07-7.01 (m,
157.52 (d, J = 238.6 Hz),





1201
504.2272;
2H), 6.99-6.92 (m,
156.33,






found,
2H), 6.87 (d, J = 5.2 Hz,
155.87 (d, J = 2.2 Hz),






504.2282
1H), 5.02 (dq, J = 9.6,
155.35,







6.4 Hz, 1H),
148.73,







4.62 (dt, J = 10.7, 7.6 Hz,
140.54,







1H), 4.32 (dd, J = 9.6,
130.32,







7.3 Hz, 1H),
117.56 (d, J = 8.0 Hz),







3.94 (s, 3H), 3.54 (ddd, J = 7.1,
115.63 (d, J = 23.0 Hz),







5.2, 1.7 Hz,
109.51, 83.79,







1H), 3.25 (dd, J = 8.7,
83.04, 76.24,







6.6 Hz, 1H),
72.70, 56.07,







3.05 (dd, J = 8.7, 6.1 Hz,
51.28, 33.30,







1H), 2.47-2.35 (m,
28.71, 27.69,







1H), 2.22 (dddd, J = 15.8,
19.37, 19.23,







10.0, 8.4, 5.3 Hz,
18.24, 18.12;







1H),
19F NMR







1.83-1.64 (m, 3H),
(CDCl3) δ −123.24







1.50-1.39 (m, 1H), 1.36 (d, J = 6.4 Hz,








3H),








1.03 (ddt, J = 16.0, 6.7,








1.9 Hz, 1H), 0.80 (d,








J = 6.7 Hz, 3H),








0.76 (d, J = 6.7 Hz, 3H)



F56
Off-White
131-133
3369,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Solid

2954,
(m/z)
12.05 (s, 1H),
(CDCl3) δ





1743,
[M]+
8.46 (d, J = 8.2 Hz, 1H),
171.92,





1650,
calcd for
7.98 (d, J = 5.2 Hz,
168.69,





1503,
C26H33FN2O7,
1H), 7.00-6.92 (m,
157.56 (d, J = 239.2 Hz),





1202
504.2272;
2H), 6.91-6.84 (m,
155.36,






found,
3H), 4.92 (dq, J = 9.6,
153.66 (d, J = 2.5 Hz),






504.2294
6.4 Hz, 1H),
148.73,







4.63 (dt, J = 10.7, 7.6 Hz,
140.54,







1H), 4.27 (ddd, J = 7.1,
130.34,







5.3, 1.8 Hz, 1H),
117.95 (d, J = 7.8 Hz),







3.94 (s, 3H),
115.89 (d, J = 23.3 Hz),







3.65-3.52 (m, 2H),
109.50, 84.24,







3.41 (dd, J = 8.6, 6.6 Hz,
83.32, 80.79,







1H), 2.43-2.31 (m,
73.06, 56.08,







1H), 2.12 (dddd, J = 15.8,
51.22, 33.22,







10.2, 7.9, 5.3 Hz,
29.03, 28.18,







1H),
19.39, 19.31,







1.88-1.60 (m, 3H), 1.47 (d, J = 6.3 Hz,
18.19, 17.96;







3H),
19F NMR







1.42-1.29 (m, 1H),
(CDCl3) δ −122.87







1.04 (ddt, J = 16.1, 7.8,








1.9 Hz, 1H), 0.85 (d,








J = 6.7 Hz, 3H),








0.81 (d, J = 6.7 Hz, 3H)



F57
Flaky White
—
3366,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Solid

2953,
(m/z)
12.07 (d, J = 0.6 Hz,
(CDCl3) δ





2872,
[M + Na]+
1H), 8.48 (d, J = 8.2 Hz,
171.99,





1745,
calcd for
1H), 8.00 (d, J = 5.1 Hz,
168.66,





1506,
C27H36N2NaO8,
1H),
155.36,





1208
539.2364;
7.09-6.98 (m, 2H), 6.87 (d,
154.19,






found,
J = 5.2 Hz, 1H),
153.96,






539.2365
6.84-6.78 (m, 2H),
148.74,







5.01 (dq, J = 9.5, 6.4 Hz,
140.53,







1H), 4.61 (dt, J = 10.8,
130.38,







7.6 Hz, 1H),
117.54,







4.29 (dd, J = 9.6, 7.2 Hz,
114.42,







1H), 3.95 (s, 3H),
109.48, 83.93,







3.78 (s, 3H),
83.07, 76.38,







3.54 (ddd, J = 7.2, 5.2, 1.7 Hz,
72.97, 56.08,







1H), 3.25 (dd, J = 8.8,
55.69, 51.30,







6.7 Hz, 1H),
33.38, 28.74,







3.09 (dd, J = 8.8, 6.2 Hz,
27.79, 19.42,







1H), 2.50-2.34 (m,
19.28, 18.27,







1H), 2.28-2.12 (m,
18.18







1H), 1.84-1.66 (m,








3H), 1.49-1.38 (m,








1H), 1.37 (d, J = 6.4 Hz,








3H), 1.03 (dd, J = 16.1,








6.9 Hz, 1H),








0.80 (dd, J = 18.7,








6.7 Hz, 6H)



F58
Purple
—
3381,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Semi-Solid

2956,
(m/z)
8.57-8.47 (m, 1H),
(CDCl3) δ





2875,
[M + Na]+
8.34 (d, J = 5.4 Hz,
172.46,





1773,
calcd for
1H), 7.01 (d, J = 5.5 Hz,
168.91,





1745,
C26H35F3N2NaO8,
1H),
162.40,





1680,
583.2238;
6.56-6.36 (m, 1H),
159.44,





1510,
found,
5.99-5.79 (m, 1H),
146.69,





1119
583.2244
4.91-4.73 (m, 1H),
141.37,







4.66-4.54 (m, 1H),
137.50,







4.53-4.40 (m, 1H),
136.91,







4.34-4.15 (m, 1H), 3.91 (s, 3H),
118.22,







3.50-3.35 (m, 2H),
117.88,







3.28 (dd, J = 8.7, 6.6 Hz,
109.81, 84.33,







1H), 3.08 (dd, J = 8.7,
84.01, 75.68,







6.2 Hz, 1H),
72.39, 71.02,







2.40 (s, 3H),
56.29, 51.31,







2.38-2.31 (m, 1H),
33.57, 28.82,







2.23-2.06 (m, 1H), 1.80 (dp, J = 13.2,
27.54, 20.75,







6.7 Hz, 1H),
19.48, 19.40,







1.69-1.59 (m, 3H),
18.18, 17.93;







1.38 (d, J = 6.3 Hz,
19F NMR







3H), 1.36-1.26 (m,
(CDCl3) δ −64.22







1H), 0.89 (dd, J = 6.6,








2.6 Hz, 6H)



F59
Light
—
3381,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Yellow

2955,
(m/z)
8.31 (d, J = 8.0 Hz,
(CDCl3) δ



Semi-Solid

2875,
[M + Na]+
1H), 8.28 (d, J = 5.3 Hz,
172.59,





1748,
calcd for
1H), 6.95 (d, J = 5.5 Hz,
170.31,





1678,
C27H37F3N2NaO9,
1H),
162.99,





1504,
613.2343;
6.42 (ddq, J = 15.7, 4.0,
160.28,





1310,
found,
2.1 Hz, 1H),
145.74,





1115
613.2349
5.95-5.84 (m, 1H), 5.74 (s,
144.02,







2H), 4.84 (dq, J = 9.3,
142.37,







6.3 Hz, 1H),
136.93,







4.61 (dt, J = 10.8, 7.6 Hz,
117.89,







1H), 4.55-4.44 (m,
109.61, 89.55,







1H), 4.29 (dt, J = 15.3,
84.35, 84.02,







4.1 Hz, 1H),
76.70, 75.67,







3.91 (s, 3H),
72.38, 71.03,







3.45 (dd, J = 9.5, 7.2 Hz,
56.19, 51.60,







1H), 3.41-3.35 (m,
33.36, 28.83,







1H), 3.28 (dd, J = 8.7,
27.52, 20.89,







6.6 Hz, 1H),
19.49, 19.41,







3.08 (dd, J = 8.7, 6.2 Hz,
18.23, 17.95;







1H), 2.38 (dt, J = 13.5,
19F NMR







6.7 Hz, 1H),
(CDCl3) δ







2.21-2.10 (m, 1H),
−64.23 (p, J = 3.3 Hz)







2.08 (s, 3H), 1.80 (dt,








J = 13.2, 6.6 Hz, 1H),








1.71-1.60 (m, 2H),








1.39 (d, J = 6.3 Hz,








3H), 1.37-1.29 (m,








1H), 0.98-0.88 (m, J = 7.3 Hz,








1H),








0.90 (dd, J = 6.7, 3.0 Hz,








6H)



F60
Yellow Oil
—
3384,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2946,
(m/z)
8.32 (d, J = 8.0 Hz,
(CDCl3) δ





1751,
[M]+
1H), 8.28 (d, J = 5.4 Hz,
172.61,





1677,
calcd for
1H),
170.42,





1502,
C32H35FN2O10,
7.07-7.01 (m, 2H),
163.14,





1200,
626.2276;
6.97-6.89 (m, 3H),
160.42,





1035
found,
6.83-6.73 (m, 4H), 5.74 (s, 2H),
157.82 (d, J = 239.1 Hz),






626.2306
5.09 (dq, J = 9.5, 6.4 Hz,
155.93 (d, J = 2.7 Hz),







1H), 4.67 (dt, J = 10.8,
154.76,







7.6 Hz, 1H),
151.58,







4.52 (dd, J = 9.6, 7.4 Hz,
145.86,







1H), 4.35 (ddd, J = 7.2,
144.19,







5.2, 1.8 Hz,
142.40,







1H), 3.91 (s, 3H),
118.68,







3.74 (s, 3H), 2.42 (dt,
117.96 (d, J = 8.0 Hz),







J = 13.8, 7.0 Hz, 1H),
115.92 (d, J = 23.0 Hz),







2.30-2.15 (m, 1H),
114.73,







2.07 (s, 3H),
109.80, 89.65,







1.96-1.82 (m, 1H),
84.15, 83.75,







1.82-1.68 (m, 1H), 1.42 (d,
72.40, 56.33,







J = 6.4 Hz, 3H),
55.77, 51.72,







1.41-1.31 (m, 1H),
33.45, 28.26,







1.11 (ddt, J = 16.2, 8.2,
21.01, 18.51,







1.8 Hz, 1H)
18.34;








19F NMR








(CDCl3) δ−122.77


F61
Yellow Oil
—
3384,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2954,
(m/z)
8.33 (d, J = 8.0 Hz,
(CDCl3) δ





1750,
[M]+
1H), 8.28 (d, J = 5.4 Hz,
172.57,





1678,
calcd for
1H),
170.29,





1503,
C29H37FN2O9,
7.06-7.00 (m, 2H),
162.99,





1200
576.2483;
6.99-6.92 (m, 3H), 5.74 (s, 2H),
160.28,






found
5.00 (dq, J = 9.6, 6.4 Hz,
157.51 (d, J = 238.8 Hz),






576.2508
1H), 4.63 (dt, J = 10.8,
155.91 (d, J = 2.2 Hz),







7.6 Hz, 1H),
145.73,







4.31 (dd, J = 9.6, 7.3 Hz,
144.03,







1H), 3.91 (s, 3H),
142.35,







3.53 (ddd, J = 7.2,
117.56 (d, J = 8.0 Hz),







5.2, 1.7 Hz, 1H),
115.62 (d, J = 22.9 Hz),







3.25 (dd, J = 8.8, 6.6 Hz,
109.65, 89.52,







1H), 3.04 (dd, J = 8.8,
83.86, 83.13,







6.2 Hz, 1H),
76.24, 72.44,







2.47-2.32 (m, 1H),
56.20, 51.64,







2.20 (dddd, J = 15.6, 10.4,
33.39, 28.72,







8.3, 5.3 Hz, 1H),
27.78, 20.87,







2.07 (s, 3H),
19.37, 19.23,







1.83-1.61 (m, 3H),
18.32, 18.12;







1.43-1.33 (m, 1H), 1.35 (d, J = 6.4 Hz,
19F NMR







3H),
(CDCl3) δ−123.37







1.02 (ddt, J = 16.0, 7.2,








1.9 Hz, 1H), 0.80 (d,








J = 6.7 Hz, 3H),








0.75 (d, J = 6.7 Hz, 3H)



F62
Yellow Oil
—
3381,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2954,
(m/z)
8.38 (d, J = 8.0 Hz,
(CDCl3) δ





1747,
[M]+
1H), 8.27 (d, J = 5.4 Hz,
176.26,





1678,
calcd for
1H),
172.57,





1503,
C31H41FN2O9,
7.06-7.01 (m, 2H),
162.96,





1201
604.2796;
6.98-6.92 (m, 3H),
160.26,






found,
5.80-5.73 (m, 2H), 5.00 (dq, J = 9.6,
157.51 (d, J = 238.8 Hz),






604.2811
6.4 Hz, 1H),
155.91 (d, J = 2.2 Hz),







4.63 (dt, J = 10.8, 7.6 Hz,
145.59,







1H), 4.31 (dd, J = 9.6,
144.25,







7.3 Hz, 1H),
142.02,







3.89 (s, 3H), 3.53 (ddd, J = 7.1,
117.57 (d, J = 8.0 Hz),







5.2, 1.7 Hz,
115.62 (d, J = 23.1 Hz),







1H), 3.25 (dd, J = 8.8,
109.58, 89.88,







6.6 Hz, 1H),
83.87, 83.13,







3.04 (dd, J = 8.8, 6.2 Hz,
76.25, 72.43,







1H), 2.54 (h, J = 7.0 Hz,
56.14, 51.63,







1H),
33.86, 33.41,







2.46-2.36 (m, 1H), 2.20 (dddd,
28.72, 27.78,







J = 11.3, 10.0, 8.4,
19.37, 19.24,







5.2 Hz, 1H),
18.68, 18.33,







1.85-1.59 (m, 3H),
18.12;







1.43-1.33 (m, 1H), 1.35 (d,
19F NMR







J = 6.4 Hz, 3H),
(CDCl3) δ−123.38







1.14 (d, J = 7.0 Hz, 6H),








1.03 (ddt, J = 16.5,








7.7, 2.1 Hz, 1H),








0.80 (d, J = 6.7 Hz, 3H),








0.75 (d, J = 6.7 Hz,








3H);



F63
Off-White
139-141
3371,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Solid

2959,
(m/z)
8.31 (d, J = 8.0 Hz,
(CDCl3) δ





1747,
[M]+
1H), 8.27 (d, J = 5.4 Hz,
172.54,





1676,
calcd for
1H),
170.28,





1503,
C29H37FN2O9,
7.00-6.90 (m, 3H),
163.00,





1202
576.2483;
6.92-6.84 (m, 2H), 5.74 (s, 2H),
160.27,






found,
4.89 (dq, J = 9.7, 6.4 Hz,
157.54 (d, J = 239.0 Hz),






576.2489
1H), 4.65 (dt, J = 10.8,
153.71 (d, J = 2.2 Hz),







7.6 Hz, 1H),
145.73,







4.26 (ddd, J = 7.2,
144.01,







5.3, 1.7 Hz, 1H),
142.34,







3.91 (s, 3H),
117.96 (d, J = 8.0 Hz),







3.67-3.49 (m, 2H), 3.40 (dd, J = 8.6,
115.86 (d, J = 23.1 Hz),







6.6 Hz, 1H),
109.63, 89.52,







2.42-2.29 (m, 1H),
84.32, 83.38,







2.07 (s, 3H),
80.77, 72.79,







1.88-1.55 (m, 3H), 1.45 (d, J = 6.4 Hz,
56.19, 51.56,







3H),
33.30, 29.02,







1.37-1.22 (m, 2H),
28.26, 20.88,







1.03 (ddt, J = 16.0, 7.8,
19.39, 19.31,







1.8 Hz, 1H), 0.84 (d,
18.25, 17.95;







J = 6.7 Hz, 3H),
19F NMR







0.81 (d, J = 6.7 Hz, 3H)
(CDCl3) δ−122.98


F64
Colorless
84-86
3366,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Solid

2949,
(m/z)
12.05 (s, 1H),
(CDCl3) δ





1649,
[M]+
8.48 (d, J = 8.1 Hz, 1H),
171.90,





1505,
calcd for
7.98 (d, J = 5.2 Hz,
168.71,





1212,
C30H34N2O9,
1H), 7.07-6.98 (m,
155.36,






566.2264;
2H), 6.89-6.71 (m,
154.60,






found,
7H), 5.09 (dq, J = 9.6,
154.43,






566.2281
6.4 Hz, 1H),
153.86,







4.65 (dt, J = 10.8, 7.6 Hz,
151.58,







1H), 4.50 (dd, J = 9.5,
148.75,







7.3 Hz, 1H),
140.56,







4.36 (ddd, J = 7.2, 5.1, 1.7 Hz,
130.31,







1H), 3.93 (s, 3H),
118.65,







3.75 (s, 3H), 3.73 (s,
117.80,







3H), 2.41 (dt, J = 13.8,
114.58,







7.0 Hz, 1H),
114.53,







2.29-2.14 (m, 1H),
109.54 84.08,







1.97-1.83 (m, 1H),
83.63, 72.76,







1.83-1.69 (m, 1H),
56.08, 55.64,







1.45 (d, J = 6.4 Hz,
51.24, 33.27,







3H), 1.45-1.34 (m,
28.06, 18.31,







1H), 1.10 (ddt, J = 16.4,
18.27, 14.21







7.9, 1.8 Hz, 1H)



F65
Colorless
70-72
3367,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Solid

2953,
(m/z)
12.07 (s, 1H),
(CDCl3) δ





1742,
[M]+
8.47 (d, J = 8.1 Hz, 1H),
171.95,





1649,
calcd for
7.97 (d, J = 5.2 Hz,
168.68,





1504,
C27H36N2O8,
1H), 6.92-6.80 (m,
155.33,





1213
516.2472;
5H), 4.91 (dq, J = 9.6,
154.36,






found,
6.3 Hz, 1H),
151.44,






516.2483
4.63 (dt, J = 10.8, 7.6 Hz,
148.71,







1H), 4.23 (ddd, J = 7.0,
140.53,







5.1, 1.7 Hz, 1H),
130.33,







3.93 (s, 3H), 3.76 (s,
118.25,







3H), 3.66-3.56 (m,
114.62,







2H), 3.41 (dd, J = 8.6,
109.50, 84.59,







6.6 Hz, 1H),
83.30, 80.75,







2.36 (dt, J = 13.6, 7.3 Hz,
73.11, 56.07,







1H), 2.12 (dddd, J = 15.8,
55.65, 51.23,







10.3, 7.9, 5.1 Hz,
33.24, 29.06,







1H),
28.03, 19.45,







1.88-1.74 (m, 2H),
19.36, 18.20,







1.76-1.59 (m, 1H),
18.00







1.47 (d, J = 6.4 Hz,








3H),








1.40-1.28 (m, 1H),








0.98 (ddt, J = 16.2, 8.1,








1.7 Hz, 1H), 0.87 (d,








J = 6.6 Hz, 3H),








0.84 (d, J = 6.7 Hz, 3H)



F66
Yellow Oil
—
3384,
ESIMS
1H NMR (CDCl3) δ
13C NMR





2959,
(m/z) 640.3
8.33 (d, J = 8.0 Hz,
(CDCl3) δ





1750,
([M + 2H]+)
1H), 8.27 (d, J = 5.3 Hz,
172.52,





1677,

1H),
170.30,





1504,

7.07-6.99 (m, 2H), 6.95 (d, J = 5.4 Hz,
163.01,





1203

1H),
160.28,





1036

6.86-6.72 (m, 6H), 5.74 (s,
154.56,







2H), 5.08 (dq, J = 9.5,
154.39,







6.3 Hz, 1H),
153.90,







4.67 (dt, J = 10.7, 7.6 Hz,
151.63,







1H), 4.49 (dd, J = 9.6,
145.74,







7.3 Hz, 1H),
144.03,







4.35 (ddd, J = 7.3, 5.2, 1.7 Hz,
142.29,







1H), 3.90 (s, 3H),
118.68,







3.75 (s, 3H), 3.73 (s,
117.80,







3H), 2.42 (dt, J = 13.8,
114.56,







7.0 Hz, 1H),
114.52,







2.22 (dddd, J = 15.8,
109.67, 89.51,







10.3, 8.0, 5.3 Hz,
84.18, 83.70,







1H), 2.07 (s, 3H),
72.50, 56.20,







1.94-1.82 (m, 1H),
55.66, 51.60,







1.82-1.68 (m, 1H),
33.35, 28.13,







1.43 (d, J = 6.4 Hz,
20.89, 18.39,







3H), 1.40-1.28 (m,
18.26







1H), 1.10 (ddt, J = 16.2,








7.9, 1.9 Hz, 1H)



F67
Yellow Oil
—
3375,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2944,
(m/z)
8.38 (d, J = 8.0 Hz,
(CDCl3) δ





1747,
[M]+
1H), 8.27 (d, J = 5.3 Hz,
176.27,





1678,
calcd for
1H),
172.52,





1505,
C35H42N2O11,
7.07-6.99 (m, 2H), 6.94 (d, J = 5.4 Hz,
162.98,





1214,
666.2789;
1H),
160.26,





1036
found,
6.86-6.73 (m, 6H),
154.57,






666.2793
5.80-5.74 (m, 2H),
154.39,







5.08 (dq, J = 9.5, 6.4 Hz,
153.91,







1H), 4.67 (dt, J = 10.7,
151.64,







7.6 Hz, 1H),
145.60,







4.49 (dd, J = 9.6, 7.4 Hz,
144.26,







1H), 4.35 (ddd, J = 7.2,
141.97,







5.1, 1.7 Hz,
118.68,







1H), 3.89 (s, 3H),
117.81,







3.75 (s, 3H), 3.74 (s,
114.56,







3H), 2.62-2.47 (m,
114.52,







1H), 2.42 (dt, J = 13.8,
109.59, 89.88,







7.0 Hz, 1H),
84.19, 83.71,







2.22 (dddd, J = 15.7,
72.49, 56.15,







9.9, 7.9, 5.2 Hz, 1H),
55.65, 51.59,







1.95-1.82 (m, 1H),
33.86, 33.37,







1.81-1.69 (m, 1H),
28.14, 18.69,







1.43 (d, J = 6.4 Hz,
18.40, 18.27







3H), 1.43-1.29 (m,








1H), 1.14 (d, J = 7.0 Hz,








6H),








1.13-1.04 (m, 1H)



F68
White Solid
118-120
3376,
ESIMS
1H NMR (CDCl3) δ
13C NMR





2956,
m/z 589.3
8.31 (d, J = 8.0 Hz,
(CDCl3) δ





1751,
([M + H]+)
1H), 8.27 (d, J = 5.3 Hz,
172.56,





1679,

1H), 6.94 (d, J = 5.4 Hz,
170.28,





1506,

1H),
162.99,







6.91-6.86 (m, 2H),
160.26,







6.85-6.78 (m, 2H), 5.74 (s,
154.33,







2H), 4.89 (dq, J = 9.6,
151.50,







6.3 Hz, 1H),
145.73,







4.65 (dt, J = 10.8, 7.6 Hz,
143.99,







1H), 4.23 (ddd, J = 7.0,
142.35,







5.2, 1.7 Hz, 1H),
118.27,







3.90 (s, 3H), 3.77 (s,
114.60,







3H), 3.68-3.55 (m,
109.63, 89.52,







2H), 3.41 (dd, J = 8.7,
84.69, 83.36,







6.6 Hz, 1H),
80.75, 72.84,







2.37 (dt, J = 13.7, 7.0 Hz,
56.19, 55.65,







1H), 2.16-2.07 (m,
51.57, 33.35,







1H), 2.07 (s, 3H),
29.06, 28.09,







1.80 (dtt, J = 13.3,
20.88, 19.45,







8.5, 4.6 Hz, 2H),
19.36, 18.26,







1.73-1.55 (m, 1H),
18.00







1.45 (d, J = 6.3 Hz, 3H),








1.35-1.22 (m, 1H),








0.98 (ddt, J = 16.1,








7.9, 1.7 Hz, 1H),








0.87 (d, J = 6.7 Hz, 3H),








0.83 (d, J = 6.7 Hz,








3H)



F69
Yellow Oil
—
3383,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2956,
(m/z)
8.36 (d, J = 8.0 Hz,
(CDCl3) δ





1747,
[M]+
1H), 8.26 (d, J = 5.4 Hz,
176.24,





1678,
calcd for
1H), 6.93 (d, J = 5.4 Hz,
172.55,





1506,
C32H44N2O10,
1H),
162.96,





1216
616.2996;
6.91-6.86 (m, 2H),
160.24,






found,
6.85-6.79 (m, 2H),
154.32,






616.3006
5.80-5.74 (m, 2H),
151.50,







4.89 (dq, J = 9.6, 6.3 Hz,
145.59,







1H), 4.64 (dt, J = 10.7,
144.20,







7.6 Hz, 1H),
142.01,







4.27-4.19 (m, 1H),
118.26,







3.88 (s, 3H), 3.77 (s,
114.60,







3H), 3.64-3.57 (m,
109.56, 89.89,







2H), 3.41 (dd, J = 8.7,
84.69, 83.36,







6.6 Hz, 1H),
80.75, 72.83,







2.55 (hept, J = 7.0 Hz,
56.14, 55.65,







1H), 2.37 (dt, J = 13.7,
51.56, 33.85,







7.0 Hz, 1H),
33.36, 29.06,







2.10 (dddd, J = 15.7,
28.09, 19.45,







10.2, 8.0, 5.1 Hz,
19.36, 18.68,







1H), 1.87-1.73 (m,
18.27, 17.99







2H), 1.72-1.57 (m,








1H), 1.45 (d, J = 6.3 Hz,








3H),








1.35-1.22 (m, 1H), 1.14








(d, J = 7.0 Hz, 6H),








0.98 (ddt, J = 16.2, 7.6,








1.7 Hz, 1H), 0.87 (d,








J = 6.7 Hz, 3H),








0.83 (d, J = 6.7 Hz, 3H)



F70
White Semi-
—
3367,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Solid

2955,
(m/z)
12.09 (s, 1H),
(CDCl3) δ





2872,
[M + H]+
8.47 (d, J = 8.0 Hz, 1H),
172.05,





1744,
calcd for
7.99 (d, J = 5.2 Hz,
168.65,





1650,
C25H41N2O7,
1H), 6.87 (d, J = 5.2 Hz,
155.34,





1529
481.2908;
1H), 4.79 (dp, J = 9.6,
148.71,






found,
6.1 Hz, 1H),
140.51,






481.2922
4.58 (dt, J = 10.8, 7.6 Hz,
130.41,







1H), 3.94 (s, 3H),
109.45, 84.17,







3.81 (dt, J = 9.0, 6.6 Hz,
83.78, 75.97,







1H), 3.60 (dt, J = 8.9,
73.89, 73.30,







6.7 Hz, 1H),
56.07, 51.30,







3.43-3.33 (m, 2H),
33.35, 30.06,







3.28 (dd, J = 8.7, 6.5 Hz,
28.88, 28.39,







1H), 3.13 (dd, J = 8.7,
27.69, 22.57,







6.3 Hz, 1H),
19.54, 19.48,







2.44-2.32 (m, 1H),
18.22, 17.91,







2.21-2.07 (m, 1H),
14.05







1.81 (dq, J = 13.2, 6.6 Hz,








1H), 1.75-1.63 (m,








2H), 1.61-1.51 (m,








2H), 1.41 (t, J = 6.5 Hz,








3H),








1.39-1.24 (m, 4H),








1.00-0.80 (m, 11H)



F71
Colorless
—
3365,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Semi-Solid

2953,
(m/z)
12.09 (s, 1H),
(CDCl3) δ





2873,
[M + H]+
8.47 (d, J = 8.2 Hz, 1H),
172.06,





1744,
calcd for
7.99 (d, J = 5.2 Hz,
168.65,





1650,
C25H41N2O8,
1H), 6.87 (d, J = 5.3 Hz,
155.35,





1529,
497.2857;
1H), 4.80 (ddd, J = 8.5,
148.72,





1482
found,
6.2, 2.4 Hz,
140.51,






497.2864
1H), 4.58 (dt, J = 10.7,
130.40,







7.7 Hz, 1H),
109.46, 84.10,







3.94 (s, 3H)
83.90, 83.84,







3.93-3.81 (m 1H),
75.86, 74.16,







3.79-3.63 (m, 1H),
73.68, 73.20,







3.52-3.23 (m, 7H),
73.13, 70.40,







3.13 (dt, J = 8.7, 6.3 Hz,
70.09, 56.08,







1H), 2.41-2.32 (m,
56.01, 55.96,







1H), 2.21-2.05 (m,
51.30, 37.38,







1H), 1.92-1.60 (m,
37.28, 33.33,







5H), 1.47-1.36 (m,
28.88, 27.65,







4H), 1.15 (dd, J = 6.1,
19.54, 19.48,







2.1 Hz, 3H),
19.15, 19.12,







0.96-0.86 (m, 7H)
18.21, 17.97,








17.93


F72
Colorless
—
3377,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Semi-Solid

2952,
(m/z)
8.31 (d, J = 8.2 Hz,
(CDCl3) δ





2873,
[M + H]+
1H), 8.28 (d, J = 5.4 Hz,
172.67,





1747,
calcd for
1H), 6.95 (d, J = 5.3 Hz,
170.30,





1678,
C28H45N2O10,
1H), 5.74 (s,
162.96,





1504,
569.3069;
2H), 4.78 (dqt, J = 10.4,
160.26,





1202,
found,
6.5, 3.3 Hz,
145.74,





1099
569.3093
1H), 4.60 (dt, J = 10.7,
143.99,







7.6 Hz, 1H),
142.42,







3.91 (s, 3H),
109.58, 89.55,







3.89-3.80 (m, 1H),
84.18, 83.95,







3.77-3.71 (m, 1H),
83.89, 75.84,







3.66 (dt, J = 9.2, 6.6 Hz,
74.17, 73.70,







1H), 3.50-3.24 (m,
72.93, 72.86,







8H), 3.12 (dt, J = 8.8,
70.39, 70.08,







6.3 Hz, 1H),
56.18, 56.00,







2.43-2.33 (m, 1H),
55.96, 51.63,







2.19-2.09 (m, 1H), 2.07 (s,
37.38, 37.28,







3H), 1.88-1.73 (m,
33.42, 28.87,







2H), 1.72-1.55 (m,
27.72, 20.88,







5H), 1.35-1.28 (m,
19.55, 19.49,







1H), 1.15 (dd, J = 6.1,
19.14, 19.12,







2.1 Hz, 3H),
18.27, 17.96,







0.92 (dd, J = 6.7, 1.9 Hz,
17.92







6H), 0.89-0.81 (m,








1H)



F73
White Solid
61-63
3368,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2954,
(m/z)
12.09 (s, 1H),
(CDCl3) δ





1743,
[M]+
8.50 (d, J = 8.2 Hz, 1H),
172.10,





1650,
calcd for
7.96 (d, J = 5.3 Hz,
168.62,





1529,
C26H38N2O7,
1H), 6.86 (d, J = 5.2 Hz,
155.22,





1265
490.2679;
1H), 4.74 (dp, J = 12.9,
148.60,






found,
6.4 Hz, 1H),
140.46,






490.2708
4.58 (dt, J = 10.8, 7.6 Hz,
130.28,







1H),
109.42, 83.24,







4.37-4.29 (m, 1H),
81.67, 80.96,







4.06-3.97 (m, 1H), 3.94 (s, 3H),
78.88, 73.66,







3.46-3.32 (m, 2H),
55.99, 51.27,







2.42-2.27 (m, 1H),
33.50, 33.24,







2.09 (dtd, J = 17.1,
32.73, 32.41,







7.8, 6.0, 3.2 Hz, 1H),
31.68, 23.69,







1.86-1.44 (m, 19H),
23.46, 23.38,







1.40 (d, J = 6.4 Hz,
23.31, 23.28,







3H), 0.90 (dd, J = 16.2,
18.50, 18.06







7.2 Hz, 1H)



F74
White Solid
91-93
3365,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2953,
(m/z)
12.08 (s, 1H),
(CDCl3) δ





1745,
[M]+
8.50 (d, J = 8.0 Hz, 1H),
172.01,





1650,
calcd for
7.98 (d, J = 5.2 Hz,
168.68,





1529,
C27H34N2O7,
1H), 7.30-7.21 (m,
159.76,





1492,
498.2366;
2H), 7.11-7.03 (m,
155.33,





1209
found,
2H), 6.98-6.90 (m,
148.71,






498.2355
1H), 6.86 (d, J = 5.2 Hz,
140.53,







1H), 5.02 (dq, J = 9.7,
130.32,







6.5 Hz, 1H),
129.26,







4.62 (dt, J = 10.8, 7.6 Hz,
121.18,







1H), 4.40 (dd, J = 9.5,
116.23,







7.3 Hz, 1H),
109.50, 82.55,







3.99-3.92 (m, 1H),
80.49, 79.68,







3.93 (s, 3H),
72.93, 56.06,







3.66-3.58 (m, 1H),
51.31, 33.37,







2.47-2.31 (m, 1H),
33.33, 31.76,







2.25-2.09 (m, 1H),
28.45, 23.40,







1.91-1.37 (m, 9H), 1.36 
22.96, 18.55,







(d, J = 6.3 Hz, 3H),
18.12







1.33-1.17 (m, 2H),








1.04 (dd, J = 16.1, 7.3 Hz,








1H)



F75
White Solid
68-70
3368,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2954,
(m/z)
12.07 (s, 1H),
(CDCl3) δ





1744,
[M]+
8.48 (d, J = 8.1 Hz, 1H),
172.02,





1650,
calcd for
7.97 (d, J = 5.2 Hz,
168.69,





1530,
C27H34N2O7,
1H), 7.31-7.22 (m,
157.57,





1482,
498.2366;
2H), 6.98-6.89 (m,
155.33,





1241
found,
3H), 6.85 (d, J = 5.2 Hz,
148.71,






498.2360
1H), 4.89 (dq, J = 9.6,
140.53,







6.4 Hz, 1H),
130.33,







4.63 (dt, J = 10.8, 7.6 Hz,
129.50,







1H), 4.38-4.30 (m,
121.21,







1H), 4.27 (tt, J = 5.3,
116.52,







3.6 Hz, 1H), 3.93 (s,
109.50, 83.74,







3H), 3.74 (dd, J = 9.6,
82.77, 80.97,







7.1 Hz, 1H),
73.29, 56.06,







2.41-2.28 (m, 1H),
51.27, 33.16,







2.25-2.09 (m, 1H),
32.89, 32.42,







1.90-1.76 (m, 1H),
28.09, 23.11,







1.76-1.48 (m, 8H),
18.22, 18.09







1.46 (d, J = 6.4 Hz, 3H),








1.44-1.28 (m, 2H),








1.03 (ddt, J = 16.2,








7.9, 1.8 Hz, 1H)



F76
Thick
—
3379,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Yellow Oil

2954,
(m/z)
8.38 (d, J = 8.1 Hz,
(CDCl3) δ





1745,
[M]+
1H), 8.26 (d, J = 5.4 Hz,
176.21,





1678,
calcd for
1H), 6.94 (d, J = 5.4 Hz,
172.75,





1504,
C31H46N2O9,
1H),
162.92,





1209
590.3203;
5.81-5.73 (m, 2H),
160.23,






found,
4.73 (dq, J = 8.7, 6.4 Hz,
145.58,






590.3216
1H), 4.60 (dt, J = 10.7,
144.18,







7.5 Hz, 1H),
142.09,







4.33 (ddd, J = 7.9,
109.52, 89.90,







4.2, 2.2 Hz, 1H),
83.28, 81.82,







4.02 (qd, J = 5.6, 4.1 Hz,
81.08, 78.94,







1H), 3.89 (s, 3H),
73.43, 56.12,







3.46-3.36 (m, 2H),
51.65, 33.84,







2.55 (hept, J = 7.0 Hz,
33.53, 33.47,







1H), 2.37 (dtd, J = 13.6,
32.78, 32.44,







6.8, 1.7 Hz,
31.74, 28.39,







1H), 2.16-2.01 (m,
23.71, 23.41,







1H), 1.85-1.44 (m,
23.34, 23.31,







18H), 1.38 (d, J = 6.4 Hz,
18.66, 18.60,







3H), 1.32 (dt, J = 10.8,
18.09







2.3 Hz, 1H),








1.14 (d, J = 7.0 Hz,








6H), 0.90 (ddt, J = 16.3,








7.5, 1.9 Hz, 1H)



F77
White Solid
73-75
3379,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2953,
(m/z)
8.53 (d, J = 7.8 Hz,
(CDCl3) δ





1772,
[M]+
1H), 8.32 (d, J = 5.4 Hz,
172.65,





1679,
calcd for
1H), 7.00 (d, J = 5.5 Hz,
168.87,





1508,
C28H40N2O8,
1H), 4.72 (dq,
162.37,





1198
532.2785;
J = 8.1, 6.2 Hz, 1H),
159.42,






found,
4.58 (ddd, J = 10.8,
146.68,






532.2807
8.4, 7.3 Hz, 1H),
141.43,







4.32 (qd, J = 5.0, 3.3 Hz,
137.47,







1H), 4.01 (qd, J = 5.4,
109.78, 83.30,







3.6 Hz, 1H),
81.85, 81.07,







3.90 (s, 3H),
78.97, 73.46,







3.46-3.34 (m, 2H), 2.40 (s, 3H),
56.28, 51.38,







2.39-2.30 (m, 1H),
33.67, 33.52,







2.14-2.01 (m, 1H),
32.80, 32.45,







1.85-1.43 (m, 18H),
31.75, 28.41,







1.37 (d, J = 6.4 Hz,
23.72, 23.41,







3H), 1.34-1.26 (m,
23.34, 23.31,







1H), 0.95-0.83 (m,
20.74, 18.57,







1H)
18.08


F78
Pale Yellow
—
3375,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Oil

2951,
(m/z)
8.33 (d, J = 8.0 Hz,
(CDCl3) δ





1749,
[M]+
1H), 8.28 (d, J = 5.3 Hz,
172.65,





1677,
calcd for
1H),
170.30,





1493,
C30H38N2O9,
7.30-7.22 (m, 2H),
162.98,





1201
570.2577;
7.10-7.04 (m, 2H),
160.28,






found,
6.98-6.90 (m, 2H),
159.80,






570.2584
5.77-5.71 (m, 2H), 5.00 (dq, J = 9.6,
145.73,







6.4 Hz, 1H),
144.03,







4.64 (dt, J = 10.8, 7.6 Hz,
142.37,







1H), 4.39 (dd, J = 9.6,
129.25,







7.4 Hz, 1H),
121.13,







3.95 (tt, J = 5.4, 3.4 Hz,
116.25,







1H), 3.91 (s, 3H),
109.62, 89.55,







3.61 (ddd, J = 7.2,
82.62, 80.59,







5.2, 1.8 Hz, 1H),
79.69, 72.70,







2.42 (dtd, J = 13.6, 6.8,
56.19, 51.66,







1.6 Hz, 1H),
33.47, 33.36,







2.25-2.09 (m, 1H), 2.07 (s,
31.77, 28.55,







3H), 1.86-1.49 (m,
23.40, 22.97,







5H), 1.49-1.35 (m,
20.88, 18.63,







5H), 1.34 (d, J = 6.4 Hz,
18.12







3H),








1.35-1.29 (m, 1H), 1.03 (ddt, J = 15.9,








7.6, 2.0 Hz,








1H)



F79
Pale Yellow
—
3375,
ESIMS
1H NMR (CDCl3) δ
13C NMR



Oil

2944,
m/z 599.3
8.38 (d, J = 8.1 Hz,
(CDCl3) δ





1745,
([M + H]+)
1H), 8.27 (d, J = 5.3 Hz,
176.26,





1676,

1H),
172.64,





1492,

7.30-7.23 (m, 2H),
162.95,





1205

7.10-7.03 (m, 2H),
160.26,







6.97-6.91 (m, 2H),
159.80,







5.81-5.73 (m, 2H), 5.01 (dq, J = 9.6,
145.59,







6.4 Hz, 1H),
144.24,







4.63 (dt, J = 10.8, 7.6 Hz,
142.04,







1H), 4.39 (dd, J = 9.6,
129.25,







7.4 Hz, 1H),
121.13,







3.95 (tt, J = 5.4, 3.4 Hz,
116.25,







1H), 3.89 (s, 3H),
109.56, 89.90,







3.61 (ddd, J = 7.2,
82.64, 80.59,







5.2, 1.8 Hz, 1H),
79.68, 72.68,







2.55 (hept, J = 7.0 Hz,
56.14, 51.65,







1H), 2.42 (dtd, J = 13.6,
33.86, 33.48,







6.8, 1.6 Hz,
33.37, 31.77,







1H), 2.24-2.09 (m,
28.55, 23.40,







1H), 1.85-1.49 (m,
22.97, 18.68,







5H), 1.49-1.35 (m,
18.63, 18.12







5H), 1.34 (d, J = 6.4 Hz,








3H),








1.34-1.28 (m, 1H), 1.14 








(d, J = 7.1 Hz, 6H),








1.04 (ddt, J = 15.9, 7.5,








1.9 Hz, 1H)



F80
White Solid
148-149
3373,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2952,
(m/z)
8.31 (d, J = 8.1 Hz,
(CDCl3) δ





1749,
[M]+
1H), 8.27 (d, J = 5.3 Hz,
172.64,





1677,
calcd for
1H),
170.29,





1494,
C30H38N2O9,
7.31-7.23 (m, 2H),
162.99,





1202
570.2577;
6.99-6.89 (m, 4H), 5.74 (s, 2H),
160.26,






found,
4.87 (dq, J = 9.6, 6.4 Hz,
157.62,






570.2577
1H), 4.65 (dt, J = 10.8,
145.73,







7.6 Hz, 1H),
143.99,







4.33 (ddd, J = 7.0,
142.36,







5.2, 1.7 Hz, 1H),
129.48,







4.26 (td, J = 5.3, 2.8 Hz,
121.16,







1H), 3.90 (s, 3H),
116.55,







3.74 (dd, J = 9.6, 7.1 Hz,
109.62, 89.52,







1H), 2.36 (dt, J = 13.7,
83.74, 82.87,







7.0 Hz, 1H),
81.03, 73.03,







2.24-2.09 (m, 1H),
56.19, 51.61,







2.07 (s, 3H),
33.28, 32.89,







1.89-1.75 (m, 1H),
32.42, 28.16,







1.75-1.45 (m, 7H), 1.45 (d,
23.11, 20.88,







J = 6.4 Hz, 3H),
18.29, 18.09







1.45-1.36 (m, 2H),








1.35-1.25 (m, 1H),








1.03 (ddt, J = 16.0, 7.7,








1.8 Hz, 1H)



F81
Thick
—
3373,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Colorless

2952,
(m/z)
8.53 (d, J = 8.4 Hz,
(CDCl3) δ



Oil

1746,
[M]+
1H), 8.34 (d, J = 5.4 Hz,
172.53,





1679,
calcd for
1H),
168.90,





1493,
C29H36N2O8,
7.30-7.22 (m, 2H),
162.40,





1198
540.2472;
7.09-7.03 (m, 2H), 7.00 (d, J = 5.5 Hz,
159.79,






found,
1H),
159.45,






540.2464
6.97-6.92 (m, 1H),
146.69,







5.00 (dq, J = 9.7, 6.4 Hz,
141.41,







1H), 4.68-4.57 (m,
137.52,







1H), 4.37 (dd, J = 9.7,
129.26,







7.4 Hz, 1H),
121.13,







3.98-3.92 (m, 1H),
116.26,







3.91 (s, 3H), 3.60 (ddd, J = 7.3,
109.81, 82.62,







5.2, 1.8 Hz,
80.60, 79.70,







1H), 2.40 (s, 3H),
72.71, 56.29,







2.24-2.07 (m, 1H),
51.37, 33.36,







1.83-1.49 (m, 6H),
31.77, 28.57,







1.49-1.34 (m, 5H),
23.40, 22.96,







1.33 (d, J = 6.4 Hz,
20.75, 18.59,







3H), 1.34-1.28 (m,
18.10, 14.21







1H); 1.07-0.99 (m,








1H)



F82
Colorless
—
3367,
HRMS-ESI
1H NMR (600 MHz,
13C NMR (151 MHz,



Semi-Solid

2954,
(m/z)
CDCl3) δ 12.06 (s,
CDCl3)





2872,
[M + Na]+
1H), 8.48 (d, J = 8.1 Hz,
δ 172.00,





1744,
calcd for
1H), 8.00 (d, J = 5.2 Hz,
168.67,





1650,
C27H36N2NaO7,
1H), 7.06 (d,
157.65,





1508,
523.2415;
J = 8.6 Hz, 2H),
155.37,





1207
found,
6.98 (d, J = 8.6 Hz, 2H),
148.75,






523.2409
6.87 (d, J = 5.3 Hz,
140.53,







1H), 5.01 (dq, J = 9.5,
130.57,







6.4 Hz, 1H),
130.39,







4.61 (dt, J = 10.8, 7.7 Hz,
129.79,







1H), 4.37 (dd, J = 9.6,
116.32,







7.3 Hz, 1H),
109.49, 83.12,







3.94 (s, 3H), 3.54 (ddd, J = 7.2,
83.04, 76.45,







5.3, 1.7 Hz,
73.00, 56.08,







1H), 3.24 (dd, J = 8.8,
51.31, 33.39,







6.6 Hz, 1H),
28.73, 27.90,







3.08 (dd, J = 8.8, 6.2 Hz,
20.50, 19.40,







1H), 2.41 (dt, J = 13.7,
19.25, 18.29,







6.6 Hz, 1H),
18.12







2.29 (s, 3H),








2.27-2.16 (m, 1H),








1.87-1.66 (m, 3H),








1.47-1.37 (m, 1H), 1.35 (d,








J = 6.4 Hz, 3H),








1.07-0.99 (m, 1H),








0.81 (d, J = 6.7 Hz, 3H),








0.76 (d, J = 6.7 Hz,








3H)



F83
Brownish
—
3380,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Semi-Solid

2952,
(m/z)
8.52 (d, J = 8.9 Hz,
(CDCl3) δ





2873,
[M + H]+
1H), 8.33 (d, J = 5.3 Hz,
172.54,





1771,
calcd for
1H), 7.00 (d, J = 5.2 Hz,
168.91,





1743,
C27H43N2O9,
1H),
162.38,





1677,
539.2963;
4.77 (ddd, J = 8.8, 6.0, 2.5 Hz,
159.43,





1506,
found,
1H), 4.59 (dt, J = 10.6,
146.69,





1195
539.2984
7.8 Hz, 1H),
141.40,







3.90 (s, 3H),
137.48,







3.89-3.79 (m, 1H),
109.79, 84.19,







3.76-3.61 (m, 1H),
84.17, 84.11,







3.49-3.21 (m, 7H),
83.93, 83.87,







3.12 (dt, J = 8.8, 6.3 Hz,
75.85, 74.17,







1H), 2.40 (s, 3H),
73.69, 72.93,







2.38-2.30 (m, 1H),
72.87, 70.38,







2.17-2.02 (m, 1H),
70.06, 56.29,







1.91-1.48 (m, 5H),
56.00, 55.95,







1.42-1.35 (m, 3H),
51.35, 37.38,







1.30 (dtd, J = 13.8,
37.28, 33.61,







11.5, 2.0 Hz, 1H),
28.86, 27.73,







1.15 (dd, J = 6.1, 2.0 Hz,
20.75, 19.54,







3H),
19.49, 19.14,







0.95-0.88 (m, 6H), 0.87 (d, J = 7.7 Hz,
19.12, 18.23,







1H)
17.94, 17.90


F84
White Solid
—
3367,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2954,
(m/z)
12.01 (s, 1H),
(CDCl3) δ





2871,
[M + H]+
8.46 (d, J = 8.1 Hz, 1H),
175.81,





1737,
calcd for
7.99 (d, J = 5.2 Hz,
175.51,





1650,
C28H39N2O9,
1H), 6.87 (d, J = 5.2 Hz,
171.83,





1529,
547.2650;
1H), 5.28 (dd, J = 9.8,
168.69,





1157
found,
8.1 Hz, 1H),
155.37,






547.2637
5.12-5.04 (m, 1H),
148.73,







5.01 (ddd, J = 7.8, 5.4, 2.2 Hz,
140.56,







1H), 4.66 (dt, J = 10.8,
130.28,







7.6 Hz, 1H),
109.52, 74.66,







3.94 (s, 3H),
73.70, 71.42,







2.77-2.58 (m, 2H),
56.09, 51.16,







2.47-2.35 (m, 1H),
43.87, 43.78,







2.16 (dddd, J = 15.9, 10.1,
33.12, 30.09,







7.8, 5.4 Hz, 1H),
30.00, 29.94,







1.93-1.79 (m, 5H),
29.80, 29.16,







1.78-1.63 (m, 9H),
25.77, 25.70,







1.62-1.51 (m, 4H),
18.11, 17.24







1.49-1.35 (m, 1H),








1.31 (d, J = 6.4 Hz, 3H),








1.19 (ddt, J = 16.4,








7.9, 2.3 Hz, 1H)



F85
White Solid
—
3368,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2946,
(m/z)
12.05 (s, 1H),
(CDCl3) δ





2882,
[M + H]+
8.46 (d, J = 8.1 Hz, 1H),
171.93,





1744,
calcd for
7.99 (d, J = 5.2 Hz,
168.69,





1650,
C24H33F6N2O7,
1H), 6.87 (d, J = 5.2 Hz,
155.38,





1530,
575.2186;
1H), 4.80 (pd, J = 6.3,
148.75,





1451,
found,
1.9 Hz, 1H),
140.55,





1253
575.2191
4.59 (dt, J = 10.8, 7.6 Hz,
130.34,







1H), 3.94 (s, 3H),
128.55,







3.80 (dt, J = 9.3, 6.1 Hz,
125.80,







1H), 3.69 (dt, J = 9.3,
109.50, 84.14,







6.2 Hz, 1H),
83.94, 72.86,







3.58 (dt, J = 9.4, 6.4 Hz,
71.82, 66.89,







1H), 3.42-3.34 (m,
56.09, 51.23,







3H), 2.45-2.32 (m,
33.22,







1H), 2.29-2.05 (m,
30.77 (qd, J = 28.8,







5H), 1.87-1.77 (m,
1.3 Hz),







4H), 1.70-1.61 (m,
27.52,







2H), 1.47-1.33 (m,
22.96 (dd, J = 19.1,







4H), 0.94 (dd, J = 16.2,
3.0 Hz),







7.3 Hz, 1H)
18.11, 17.90;








19F NMR








(CDCl3) δ








−66.37 (dt, J = 25.5,








11.2 Hz)


F86
Colorless
—
2954,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Semi-Solid

1751,
(m/z)
8.32 (d, J = 8.1 Hz,
(CDCl3) δ





1678,
[M + H]+
1H), 8.28 (d, J = 5.3 Hz,
172.62,





1508
calcd for
1H), 7.06 (d, J = 8.5 Hz,
170.31,






C30H41N2O9,
2H), 6.97 (d,
162.97,






573.2807;
J = 8.6 Hz, 2H),
160.28,






found,
6.95 (d, J = 5.4 Hz, 1H),
157.69,






573.2792
5.74 (s, 2H),
145.73,







4.99 (dq, J = 9.6, 6.4 Hz,
144.03,







1H), 4.63 (dt, J = 10.7,
142.38,







7.6 Hz, 1H),
130.51,







4.36 (dd, J = 9.6, 7.3 Hz,
129.77,







1H), 3.91 (s, 3H),
116.32,







3.53 (ddd, J = 7.1,
109.61, 89.55,







5.2, 1.7 Hz, 1H),
83.18, 83.12,







3.24 (dd, J = 8.8, 6.6 Hz,
76.42, 72.73,







1H), 3.08 (dd, J = 8.8,
56.19, 51.65,







6.2 Hz, 1H),
33.46, 28.72,







2.41 (dt, J = 13.8, 6.6 Hz,
27.96, 20.89,







1H), 2.29 (s, 3H),
20.50, 19.40,







2.24-2.13 (m, 1H),
19.26, 18.35,







2.07 (s, 3H),
18.12







1.86-1.65 (m, 3H),








1.43-1.35 (m, 1H), 1.34 (d,








J = 6.5 Hz, 3H),








1.03 (dd, J = 16.1, 7.4 Hz,








1H), 0.78 (dd, J = 19.4,








6.7 Hz, 6H)



F87
Colorless
—
2948,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Semi-Solid

1751,
(m/z)
8.31 (d, J = 8.1 Hz,
(CDCl3) δ





1679,
[M + H]+
1H), 8.28 (d, J = 5.3 Hz,
172.55,





1505,
calcd for
1H), 6.95 (d, J = 5.4 Hz,
170.31,





1335
C27H37F6N2O9,
1H), 5.74 (s,
163.00






647.2398;
2H), 4.83-4.74 (m,
160.28,






found,
1H), 4.61 (dt, J = 10.8,
145.74,






647.2414
7.5 Hz, 1H),
144.03,







3.91 (s, 3H), 3.80 (dt,
142.34,







J = 9.3, 6.2 Hz, 1H),
109.62, 89.53,







3.68 (dt, J = 9.2, 6.1 Hz,
84.21, 83.99,







1H), 3.58 (dt, J = 9.3,
72.59, 71.80,







6.3 Hz, 1H),
66.87, 56.19,







3.42-3.33 (m, 3H),
51.57, 33.29,







2.42-2.34 (m, 1H),
30.78 (qd, J = 28.9,







2.26-2.05 (m, 6H),
2.1 Hz),







2.07 (s, 3H),
27.60,







1.88-1.78 (m, 4H),
23.25-22.60 (m),







1.71-1.60 (m, 1H), 1.38 
20.88, 18.18,







(d, J = 6.3 Hz, 3H),
17.89;







1.36-1.22 (m, 1H),
19F NMR







0.99-0.88 (m, 1H)
CDCl3) δ








−66.38 (dt, J = 26.8,








11.1 Hz)


F88
Colorless
—
2956,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Semi-Solid

2871,
(m/z)
8.32 (d, J = 7.9 Hz,
(CDCl3) δ





1737,
[M + H]+
1H), 8.27 (d, J = 5.3 Hz,
175.85,





1678,
calcd for
1H), 6.95 (d, J = 5.4 Hz,
175.51,





1503,
C31H43N2O11,
1H), 5.74 (s,
172.43,





1157
619.2861;
2H), 5.27 (dd, J = 9.8,
170.31,






found,
8.1 Hz, 1H),
162.99,






619.2855
5.12-4.95 (m, 2H),
160.28,







4.67 (dt, J = 10.8, 7.6 Hz,
145.72,







1H), 3.91 (s, 3H),
144.07,







2.68 (dtt, J = 10.3,
142.22,







8.6, 7.0 Hz, 2H),
109.65, 89.53,







2.41 (dt, J = 13.8, 7.1 Hz,
74.77, 73.79,







1H), 2.20-2.09 (m,
71.13, 56.20,







1H), 2.07 (s, 3H),
51.51, 43.89,







1.96-1.79 (m, 5H),
43.79, 33.18,







1.79-1.64 (m, 9H),
30.08, 30.01,







1.61-1.49 (m, 4H),
29.93, 29.80,







1.43-1.32 (m, 1H),
29.22, 25.77,







1.29 (d, J = 6.4 Hz,
25.70, 20.88,







3H), 1.18 (ddt, J = 16.2,
18.18, 17.24







7.9, 2.2 Hz, 1H)



F89
Yellow Oil
—
3376,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2954,
(m/z)
8.52 (d, J = 8.2 Hz,
(CDCl3) δ





2872,
[M + H]+
1H), 8.33 (d, J = 5.4 Hz,
172.54,





1772,
calcd for
1H), 7.00 (d, J = 5.5 Hz,
168.91,





1744,
C27H43N2O8,
1H),
162.38,





1679,
523.3014;
4.77 (ddq, J = 9.0, 6.2, 3.6 Hz,
159.42,





1508,
found,
1H),
146.69,





1197
523.3055
4.67-4.50 (m, 1H), 3.90 (s, 3H),
141.42,







3.80 (dt, J = 9.0, 6.5 Hz,
137.47,







1H), 3.59 (dt, J = 8.9,
109.78, 84.25,







6.7 Hz, 1H),
83.82, 75.96,







3.42-3.21 (m, 3H),
73.87, 73.03,







3.12 (dd, J = 8.8, 6.3 Hz,
56.28, 51.35,







1H), 2.40 (s, 3H),
33.64, 30.06,







2.37-2.29 (m, 1H),
28.86, 28.39,







2.21-2.01 (m, 1H),
27.78, 22.56,







1.82 (dt, J = 13.1, 6.6 Hz,
20.75, 19.53,







2H),
19.48, 18.24,







1.69-1.55 (m, 3H),
17.88, 14.05







1.43-1.19 (m, 8H),








1.00-0.78 (m, 10H)



F90
Yellow
—
3379,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Semi-Solid

2946,
(m/z)
8.49 (d, J = 8.2 Hz,
(CDCl3) δ





2881,
[M + H]+
1H), 8.33 (d, J = 5.5 Hz,
172.43,





1772,
calcd for
1H), 7.00 (d, J = 5.5 Hz,
168.92,





1744,
C26H35F6N2O8,
1H), 4.78 (dq,
162.43,





1508,
617.2292;
J = 8.4, 6.1 Hz, 1H),
159.45,





1147
found,
4.59 (dt, J = 10.8, 7.7 Hz,
146.70,






617.2297
1H), 3.91 (s, 3H),
141.35,







3.80 (dt, J = 9.3, 6.1 Hz,
137.51,







1H), 3.68 (dt, J = 9.3,
128.55,







6.2 Hz, 1H),
109.83, 84.20,







3.57 (dt, J = 9.3, 6.3 Hz,
83.98, 72.60,







1H), 3.43-3.19 (m,
71.79, 66.88,







3H), 2.40 (s, 3H),
56.30, 51.29,







2.40-2.27 (m, 1H),
33.51,







2.23-1.97 (m, 5H),
30.78 (qd, J = 29.3,







1.88-1.67 (m, 4H),
28.8, 1.4 Hz),







1.67-1.49 (m, 2H),
27.61,







1.37 (d, J = 6.3 Hz,
22.94 (dt, J = 19.7,







3H), 1.34-1.15 (m,
2.9 Hz),







1H), 0.99-0.86 (m,
20.75, 18.13,







1H)
17.87;








19F NMR








(CDCl3) δ-








66.38 (dt, J = 25.0,








11.1 Hz)


F91
Colorless
—
3375,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Semi-Solid

2953,
(m/z)
8.49 (d, J = 8.2 Hz,
(CDCl3) δ





2871,
[M + H]+
1H), 8.33 (d, J = 5.4 Hz,
175.83





1735,
calcd for
1H), 7.01 (d, J = 5.5 Hz,
175.51,





1677,
C30H41N2O10,
1H), 5.25 (dd,
172.31,





1507,
589.2756;
J = 9.8, 8.1 Hz, 1H),
168.91,





1157
found,
5.11-4.92 (m, 2H),
162.42,






589.2769
4.66 (dt, J = 10.7, 7.7 Hz,
159.45,







1H), 3.91 (s, 3H),
146.69,







2.82-2.57 (m, 2H),
141.26,







2.42-2.34 (m, 1H),
137.52,







2.40 (s, 3H),
109.85, 74.74,







2.19-2.06 (m, 1H),
73.77, 71.15,







1.93-1.49 (m, 18H),
56.30, 51.21,







1.42-1.31 (m, 1H),
43.87, 43.78,







1.27 (dd, J = 12.1, 6.8 Hz,
30.08, 30.00,







3H), 1.17 (ddt, J = 16.1,
29.94, 29.79,







7.7, 2.3 Hz, 1H)
29.25, 25.77,








25.75, 25.69,








20.75, 18.14,








17.22


F92
Light
—
3376,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Yellow

2954,
(m/z)
8.53 (d, J = 8.5 Hz,
(CDCl3) δ



Semi-Solid

2872,
[M + H]+
1H), 8.34 (d, J = 5.4 Hz,
172.50,





1770,
calcd for
1H),
168.92,





1744,
C29H39N2O8,
7.09-7.02 (m, 2H),
162.39,





1506,
543.2701;
7.03-6.94 (m, 3H), 4.99 (dq, J = 9.6,
159.43,





1195
found,
6.4 Hz, 1H),
157.67,






543.2698
4.62 (dt, J = 10.7, 7.7 Hz,
146.70,







1H), 4.34 (dd, J = 9.7,
141.39,







7.3 Hz, 1H),
137.50,







3.91 (s, 3H), 3.52 (ddd, J = 7.1,
130.50,







5.2, 1.7 Hz,
129.76,







1H), 3.23 (dd, J = 8.8,
116.33,







6.6 Hz, 1H),
109.80, 83.18,







3.12-3.00 (m, 1H),
83.10, 76.43,







2.40 (s, 3H),
72.73, 56.29,







2.40-2.30 (m, 1H), 2.29 (s, 3H),
51.36, 33.66,







2.24-2.09 (m, 1H),
28.71, 27.97,







1.72 (ddt, J = 13.2,
20.75, 20.50,







9.5, 6.7 Hz, 3H),
19.39, 19.25,







1.62-1.53 (m, 1H),
18.31, 18.09







1.37-1.28 (m, 3H),








1.07-0.96 (m, 1H),








0.85-0.71 (m, 6H)



F93
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
7.37-7.25 (m, 10H),
(CDCl3) δ






[M + Na]+
5.89 (dd, J = 18.1,
170.26,






calcd for
10.3 Hz, 1H), 5.60 (t,
152.74,






C33H43NNaO8,
J = 10.2 Hz, 1H),
138.49,






604.2881;
5.02 (d, J = 10.9 Hz,
138.31,






found,
1H), 4.95-4.81 (m,
135.57,






604.2874
1H), 4.66-4.48 (m,
128.54,







3H), 4.43 (d, J = 11.6 Hz,
128.32,







1H), 4.08 (t, J = 9.2 Hz,
128.30,







1H), 3.41 (t, J = 9.0 Hz,
128.23,







1H),
127.69,







3.14 (q, J = 12.0 Hz, 1H),
127.56,







2.37 (dd, J = 12.3,
127.44, 83.80,







7.4 Hz, 1H), 1.49 (s,
82.89, 77.68,







18H), 1.33 (d, J = 6.3 Hz,
75.28, 74.28,







3H)
70.89, 56.96,








33.02, 27.97,








19.17


F94
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
12.10-12.02 (m,
(CDCl3) δ






[M + H]+
1H), 8.47 (d, J = 8.1 Hz,
171.97,






calcd for
1H), 7.98 (dd, J = 5.2,
168.69,






C27H37N2O7,
0.9 Hz, 1H),
157.62






501.2595;
7.32-7.24 (m, 2H),
155.35,






found,
6.93 (dddd, J = 12.2, 9.6,
148.73,






501.2603
8.3, 4.1 Hz, 3H),
140.54,







6.86 (d, J = 5.2 Hz, 1H),
130.35,







4.91 (tq, J = 9.0, 6.4 Hz,
129.50,







1H), 4.63 (dtd, J = 11.4,
121.29,







7.7, 3.9 Hz,
116.63,







1H), 4.40 (dt, J = 18.8,
109.49, 83.40,







5.4 Hz, 1H),
83.03, 73.98,







3.93 (s, 3H),
73.04, 56.07,







3.86-3.71 (m, 1H),
51.24 33.22,







3.63 (dt, J = 9.0, 6.7 Hz,
29.95, 28.24,







2H), 2.35 (dq, J = 14.9,
22.44, 18.21,







7.4 Hz, 1H)
17.93, 13.96,







2.30-2.10 (m, 1H),
9.42, 9.21







1.89-1.75 (m, 1H),








1.67-1.55 (m, 1H),








1.55-1.42 (m, 5H),








1.40-1.28 (m, 1H),








1.28-1.17 (m, 3H),








1.05 (dd, J = 16.1,








7.8 Hz, 1H), 0.87 (t, J = 7.5 Hz,








1H),








0.83-0.77 (m, 2H), 0.69 (t,








J = 7.4 Hz, 1H)



F95
Tacky
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



White Foam


(m/z)
8.31 (d, J = 8.0 Hz,
(CDCl3) δ






[M + H]+
1H), 8.27 (d, J = 5.4 Hz,
172.57,






calcd for
1H),
170.27,






C28H37N2O9, 545.2494;
7.32-7.22 (m, 2H),
163.00,






found,
7.02-6.86 (m, 4H), 5.74 (s, 2H),
160.27,






545.2506
4.91 (dq, J = 9.7, 6.4 Hz,
157.68,







1H), 4.65 (dt, J = 10.7,
145.74,







7.6 Hz, 1H),
143.99,







4.37 (t, J = 5.5 Hz,
142.35,







1H), 3.90 (s, 3H),
129.48,







3.73 (dt, J = 8.9, 6.5 Hz,
121.25,







1H),
116.69,







3.68-3.52 (m, 2H), 2.37 (dt, J = 13.6,
109.64, 89.51,







7.0 Hz, 1H),
83.41, 83.19,







2.25-2.09 (m, 1H),
75.57, 72.77,







2.07 (s, 3H),
56.19, 51.58,







1.85-1.76 (m, 1H),
33.29, 28.32,







1.64 (dq, J = 15.4, 7.5 Hz,
23.43, 20.88,







1H), 1.56-1.41 (m,
18.27, 17.92,







5H), 1.37-1.26 (m,
10.60







1H), 1.05 (dd, J = 16.1,








7.8 Hz, 1H),








0.83 (t, J = 7.4 Hz,








3H)



F96
Tacky
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



White Foam


(m/z)
8.31 (d, J = 8.0 Hz,
(CDCl3) δ






[M + Na]+
1H), 8.27 (dd, J = 5.4,
172.57,






calcd for
0.8 Hz, 1H),
170.27,






C30H40N2NaO9,
7.31-7.22 (m, 2H),
162.99,






595.2626;
6.98-6.84 (m, 4H),
160.26,






found,
5.74 (s, 2H),
157.67,






595.2659
4.96-4.82 (m, 1H), 4.65 (dtd, J = 11.4,
145.73,







7.6, 4.0 Hz,
143.99,







1H), 4.39 (dt, J = 18.7,
142.35,







5.4 Hz, 1H),
129.47,







3.90 (s, 3H),
121.23,







3.85-3.70 (m, 1H),
116.64,







3.62 (ddd, J = 9.0, 7.0, 5.1 Hz,
109.63, 89.51,







2H), 2.36 (dq, J = 14.3,
83.45, 83.12,







7.3 Hz, 1H),
73.95, 72.76,







2.28-2.10 (m, 1H),
56.19, 51.58,







2.07 (s, 3H),
33.29, 29.95,







1.89-1.75 (m, 1H),
28.24, 25.30,







1.64 (ddt, J = 15.0, 11.7,
22.43, 20.87,







7.4 Hz, 1H),
18.28, 17.92,







1.54-1.42 (m, 5H),
13.96, 9.41,







1.36-1.27 (m, 1H), 1.26 (s,
9.20







3H), 1.10-0.99 (m,








1H), 0.86 (t, J = 7.5 Hz,








1H),








0.83-0.76 (m, 2H), 0.69 (t, J = 7.4 Hz,








1H)



F97
Tacky
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



White Foam


(m/z)
8.37 (d, J = 8.1 Hz,
(CDCl3) δ






[M + H]+
1H), 8.26 (d, J = 5.4 Hz,
176.24,






calcd for
1H),
172.56,






C30H41N2O9,
7.32-7.20 (m, 2H),
162.97,






573.2807;
6.99-6.88 (m, 4H),
160.24,






found,
5.81-5.72 (m, 2H), 4.91 (dq, J = 9.6,
157.68,






573.2795
6.4 Hz, 1H),
145.60,







4.65 (dt, J = 10.7, 7.6 Hz,
144.20,







1H), 4.37 (t, J = 5.4 Hz,
142.01,







1H), 3.88 (s, 3H),
129.48,







3.73 (dt, J = 8.9, 6.5 Hz,
121.24,







1H),
116.68,







3.67-3.53 (m, 2H), 2.55 (p, J = 7.0 Hz,
109.57, 89.87,







1H), 2.37 (dt,
83.41, 83.19,







J = 13.6, 7.0 Hz, 1H),
75.57, 72.75,







2.16 (dddd, J = 15.7,
56.14 51.57,







10.1, 6.4, 4.0 Hz,
33.85, 33.30,







1H), 1.88-1.78 (m,
28.31, 23.43,







1H), 1.63 (tt, J = 16.0,
18.67, 18.27,







8.2 Hz, 1H)
17.92, 10.59







1.55-1.41 (m, 5H),








1.36-1.23 (m, 1H),








1.14 (d, J = 7.0 Hz,








6H), 1.05 (dd, J = 16.1,








7.8 Hz, 1H),








0.83 (t, J = 7.4 Hz,








3H)



F98
Tacky
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



White Foam


(m/z)
8.37 (d, J = 8.1 Hz,
(CDCl3) δ






[M + H]+
1H), 8.26 (dd, J = 5.4,
176.24,






calcd for
0.9 Hz, 1H),
172.57,






C32H45N2O9,
7.31-7.20 (m, 2H),
162.97,






601.3120;
6.99-6.84 (m, 4H),
160.24,






found,
5.83-5.73 (m, 2H),
157.67,






601.3131
4.96-4.80 (m, 1H),
145.60,







4.64 (dtd, J = 11.3, 7.6,
144.20,







3.9 Hz, 1H), 4.39 (dt,
142.02,







J = 18.7, 5.5 Hz, 1H),
129.47,







3.88 (s, 3H),
121.22,







3.84-3.72 (m, 1H),
116.63,







3.62 (ddd, J = 9.0, 6.9, 5.4 Hz,
109.58, 89.87,







2H),
83.46, 83.11,







2.62-2.47 (m, 1H), 2.36 (dq, J = 14.3,
73.95, 72.75,







7.3 Hz, 1H),
56.14, 51.57,







2.26-2.08 (m, 1H),
33.85, 33.30,







1.88-1.74 (m, 1H),
29.95, 28.33,







1.64 (ddt, J = 14.8,
28.24, 25.32,







11.5, 7.3 Hz, 1H),
25.30, 22.43,







1.53-1.40 (m, 5H),
18.68, 18.28,







1.36-1.26 (m, 1H),
17.92, 13.96,







1.23 (td, J = 8.2, 6.7,
9.41, 9.20







4.6 Hz, 3H), 1.14 (d,








J = 7.0 Hz, 6H),








1.10-1.00 (m, 1H),








0.86 (t, J = 7.5 Hz, 1H),








0.83-0.76 (m, 2H),








0.69 (t, J = 7.4 Hz,








1H)



F99
Yellow
—
3376,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Semi-Solid

2955,
(m/z)
8.37 (d, J = 8.0 Hz,
(CDCl3) δ





2872,
[M + H]+
1H), 8.27 (d, J = 5.3 Hz,
176.28,





1738,
calcd for
1H), 6.94 (d, J = 5.4 Hz,
175.84,





1679,
C33H47N2O11,
1H),
175.51,





1504,
647.3174;
5.81-5.72 (m, 2H),
172.42,





1157
found
5.27 (dd, J = 9.8, 8.1 Hz,
162.97,






647.3187
1H), 5.11-4.95 (m,
160.26,







2H), 4.66 (dt, J = 10.8,
145.58,







7.6 Hz, 1H),
144.27,







3.89 (s, 3H),
141.89,







2.74-2.62 (m, 2H), 2.55 (p,
109.60, 89.87,







J = 7.0 Hz, 1H),
74.78, 73.79,







2.40 (dt, J = 13.8, 7.1 Hz,
71.11, 56.14,







1H), 2.22-2.04 (m,
51.51, 43.89,







1H), 1.96-1.79 (m,
43.79, 33.86,







6H), 1.78-1.67 (m,
33.17, 30.08,







8H), 1.60-1.50 (m,
30.00, 29.93,







5H), 1.45-1.34 (m,
29.79, 29.21,







1H), 1.29 (d, J = 6.3 Hz,
25.77, 25.75,







3H), 1.14 (d, J = 7.0 Hz,
25.70, 18.68,







6H)
18.18, 17.24


F100
Colorless
—
3382,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Semi-Solid

2943,
(m/z)
8.36 (d, J = 8.0 Hz,
(CDCl3) δ





2880,
[M + H]+
1H), 8.27 (d, J = 5.3 Hz,
176.28,





1746,
calcd for
1H), 6.94 (d, J = 5.4 Hz,
172.55,





1678,
C29H41F6N2O9,
1H),
163.00,





1504,
675.2711;
5.84-5.72 (m, 2H),
160.28,





1253,
found,
4.78 (pd, J = 6.4, 2.2 Hz,
145.63,





1103
675.2713
1H), 4.60 (dt, J = 10.7,
144.24,







10.7, 7.5 Hz, 1H),
142.01,







3.89 (s, 3H), 3.80 (dt,
127.21 (q, J = 276.0 Hz),







J = 9.3, 6.1 Hz, 1H),
109.61, 89.89,







3.68 (dt, J = 9.1, 6.2 Hz,
84.22, 84.01,







1H), 3.58 (dt, J = 9.1,
72.59, 71.81,







6.3 Hz, 1H),
66.87, 56.16,







3.42-3.31 (m, 3H),
51.58, 33.87,







2.55 (p, J = 7.0 Hz, 1H),
33.30,







2.42-2.32 (m, 1H),
30.79 (qd, J = 28.7,







2.26-2.06 (m, 5H),
2.1 Hz),







1.86-1.79 (m, 4H),
27.60,







1.72-1.58 (m, 2H),
22.97 (dd, J = 19.7,







1.39 (d, J = 6.3 Hz,
2.9 Hz),







3H), 1.35-1.28 (m,
18.68, 18.20,







1H), 1.14 (d, J = 7.0 Hz,
17.90;







6H),
19F NMR







1.00-0.88 (m, 1H)
(CDCl3) δ-








66.40 (dt, J = 25.3,








11.2 Hz)


F101
Colorless
—
3377,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Semi-Solid

2954,
(m/z)
8.38 (d, J = 8.0 Hz,
(CDCl3) δ





2874,
[M + H]+
1H), 8.27 (d, J = 5.3 Hz,
176.26,





1745,
calcd for
1H), 7.06 (d, J = 8.4 Hz,
172.61,





1677,
C32H45N2O9,
2H), 6.98 (d,
162.95,





1506,
601.3120;
J = 8.6 Hz, 2H),
160.25,





1205
found,
6.94 (d, J = 5.4 Hz, 1H),
157.69,






601.3105
5.87-5.69 (m, 2H),
145.60,







4.99 (dq, J = 9.6, 6.4 Hz,
144.22,







1H), 4.63 (dt, J = 10.8,
142.03,







7.5 Hz, 1H),
130.49,







4.36 (dd, J = 9.6, 7.3 Hz,
129.76,







1H), 3.89 (s, 3H),
116.32,







3.53 (ddd, J = 7.2,
116.29,







5.2, 1.7 Hz, 1H),
109.57, 89.88,







3.24 (dd, J = 8.8, 6.7 Hz,
83.18, 83.11,







1H), 3.08 (dd, J = 8.8,
76.41, 72.70,







6.2 Hz, 1H),
56.14, 51.64,







2.55 (p, J = 7.0 Hz, 1H),
33.85, 33.44,







2.48-2.35 (m, 1H),
28.71, 27.94,







2.29 (s, 3H),
20.50, 19.40,







2.19 (dddd, J = 15.7, 10.3,
19.25, 18.68,







8.3, 5.3 Hz, 1H),
18.36, 18.11







1.77-1.61 (m, 3H),








1.42-1.27 (m, 4H),








1.14 (d, J = 7.0 Hz, 6H),








1.07-0.96 (m, 1H),








0.78 (dd, J = 19.4,








6.7 Hz, 6H)



F102
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.52 (d, J = 6.7 Hz,
(CDCl3) δ






[M + Na]+
1H), 8.32 (d, J = 5.4 Hz,
172.45,






calcd for
1H), 7.27 (t, J = 7.9 Hz,
168.89,






C27H34N2NaO9,
2H), 6.99 (d,
162.42,






537.2207;
J = 5.5 Hz, 1H),
159.44,






found,
6.95 (t, J = 8.7 Hz, 3H),
157.68,






537.2210
4.96-4.84 (m, 1H),
146.70,







4.64 (dt, J = 10.5, 7.9 Hz,
141.35,







1H), 4.36 (t, J = 5.5 Hz,
137.49,







1H), 3.89 (s,
129.48,







3H), 3.73 (dt, J = 8.7,
121.25,







6.5 Hz, 1H),
116.68,







3.67-3.51 (m, 2H),
109.83, 83.40,







2.47-2.26 (m, 4H),
83.20, 75.57,







2.23-2.07 (m, 1H),
72.78, 56.29,







1.86-1.74 (m, 1H),
51.30, 33.50,







1.62 (dq, J = 16.4, 9.0, 8.4 Hz,
28.34, 23.43,







1H),
20.74, 18.24,







1.55-1.40 (m, 5H),
17.90, 10.59







1.33-1.23 (m, 1H), 1.04 (dd, J = 16.0,








7.7 Hz, 1H),








0.83 (t, J = 7.4 Hz,








3H)



F103
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.52 (d, J = 6.6 Hz,
(CDCl3) δ






[M + Na]+
1H), 8.32 (d, J = 5.4 Hz,
172.45,






calcd for
1H),
168.89,






C29H38N2NaO9,
7.32-7.23 (m, 1H), 7.00 
162.42,






560.2966;
(d, J = 5.5 Hz, 1H),
159.44,






found,
6.97-6.85 (m, 3H),
157.67,






560.2954
4.88 (dtd, J = 9.5, 6.4, 3.2 Hz,
146.69,







1H), 4.63 (ddq, J = 11.6,
141.36,







8.0, 4.1 Hz,
137.50,







1H), 4.39 (dt, J = 18.8,
129.47,







18.8, 5.5 Hz, 1H),
121.23,







3.90 (s, 3H),
116.64,







3.77 (ddt, J = 13.0, 8.9,
109.82, 83.44,







6.7 Hz, 1H),
83.13, 73.95,







3.66-3.57 (m, 2H), 2.40 (s,
72.77, 56.28,







4H), 2.27-2.07 (m,
51.29, 33.51,







1H), 1.86-1.71 (m,
29.95, 28.24,







1H), 1.69-1.56 (m,
25.30, 22.43,







1H), 1.46 (dd, J = 13.0,
20.74, 17.89,







13.0, 5.7 Hz, 5H),
13.95, 9.19







1.31-1.17 (m, 5H),








1.10-0.94 (m, 1H),








0.86 (t, J = 7.5 Hz,








1H), 0.83-0.76 (m,








2H), 0.68 (t, J = 7.4 Hz,








1H)



F104
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
12.04 (d, J = 0.5 Hz,
(CDCl3) δ






[M + H]+
1H), 8.46 (d, J = 8.1 Hz,
171.88,






calcd for
1H), 7.98 (d, J = 5.2 Hz,
168.72,






C26H30F3N2O7,
1H),
157.08,






540.2032;
7.31-7.24 (m, 2H),
155.37,






found
7.03-6.94 (m, 1H),
148.74,






540.2038
6.91 (dd, J = 8.7, 1.0 Hz,
140.56,







2H), 6.87 (d, J = 5.2 Hz,
6.39 (q, J = 6.4 Hz),







1H), 6.33 (ddq, J = 15.7,
130.29,







4.2, 2.1 Hz,
129.66,







1H), 5.89-5.74 (m,
125.64 (q, J = 269.1 Hz),







1H), 4.98 (dq, J = 9.6,
121.67,







6.4 Hz, 1H),
118.43 (q, J = 34.1 Hz),







4.64 (dt, J = 10.7, 7.6 Hz,
116.55,







1H), 4.51-4.39 (m,
109.53, 83.80,







2H), 4.35-4.24 (m,
82.70, 72.39,







1H), 3.94 (s, 3H),
71.00, 56.08,







3.74 (dd, J = 9.6, 7.2 Hz,
51.20, 33.12,







1H), 2.37 (dt, J = 13.6,
28.16, 18.17,







7.1 Hz, 1H),
17.98







2.20 (tdd, J = 13.3,








6.3, 3.9 Hz, 1H),








1.90-1.75 (m, 1H),








1.73-1.62 (m, 1H),








1.47 (d, J = 6.4 Hz, 3H),








1.43-1.31 (m, 1H),








1.09 (dd, J = 16.2,








7.8 Hz, 1H)



F105
White Solid
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
12.04 (s, 1H),
(CDCl3) δ






[M + Na]+
8.46 (d, J = 8.1 Hz, 1H),
171.93,






calcd for
7.98 (d, J = 5.2 Hz,
168.70,






C26H31F3N2NaO7,
1H), 7.32-7.28 (m,
157.30,






563.1976;
1H), 6.97 (t, J = 7.4 Hz,
155.37,






found,
1H),
148.74,






563.2009
6.93-6.89 (m, 2H), 6.87 (d, J = 5.2 Hz,
140.55,







1H), 4.93 (dq,
130.31,







J = 9.6, 6.4 Hz, 1H),
129.61,







4.64 (dt, J = 10.7, 7.6 Hz,
127.14 (q, J = 276.0 Hz),







1H), 4.38 (t, J = 5.5 Hz,
121.45,







1H), 3.94 (s,
116.31,







3H), 3.80 (dt, J = 9.1,
109.51, 83.63,







6.1 Hz, 1H), 3.71 (dt,
82.48, 72.70,







J = 9.2, 5.9 Hz, 1H),
71.85, 56.08,







3.65 (dd, J = 9.6, 7.2 Hz,
51.22, 33.17,







1H), 2.36 (dt, J = 13.7,
30.54 (q, J = 28.9 Hz),







7.0 Hz, 1H),
28.25,







2.27-2.13 (m, 1H),
22.93 (q, J = 2.7 Hz),







2.03 (ddddd, J = 29.6,
18.16,







14.8, 11.3, 6.9,
17.93







3.3 Hz, 2H),








1.90-1.76 (m, 1H),








1.76-1.59 (m, 4H), 1.46 (d,








J = 6.4 Hz, 3H),








1.42-1.29 (m, 1H),








1.07 (dd, J = 16.1, 7.8 Hz,








1H)



F106
Clear Tacky
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Solid


(m/z)
8.32 (d, J = 8.0 Hz,
(CDCl3) δ






[M + H]+
1H), 8.27 (d, J = 5.4 Hz,
172.48,






calcd for
1H),
170.28,






C29H34F3N2O9,
7.31-7.23 (m, 2H),
163.02,






611.2211
7.01-6.87 (m, 4H), 6.32 (ddq, J = 15.7,
160.28,






found
4.1, 2.1 Hz,
157.14,






611.2213
1H), 5.88-5.75 (m,
145.74,







1H), 5.74 (s, 2H),
144.01,







4.96 (dq, J = 9.7, 6.4 Hz,
142.27,







1H), 4.66 (dt, J = 10.7,
136.45 (q, J = 6.4 Hz),







7.6 Hz, 1H),
129.62,







4.51-4.37 (m, 2H),
122.98 (q, J = 269.2 Hz),







4.33-4.24 (m, 1H),
121.60,







3.91 (s, 3H),
118.36 (q, J = 34.1 Hz),







3.73 (dd, J = 9.6, 7.2 Hz,
116.56,







1H), 2.37 (dt, J = 13.6,
109.67, 89.48,







13.6, 7.0 Hz, 1H),
83.87, 82.77,







2.28-2.11 (m, 1H),
72.12, 70.99,







2.07 (s, 3H), 1.80 (s,
56.19, 51.55,







1H), 1.64 (dq, J = 15.5,
33.17, 28.23,







7.7 Hz, 1H),
20.86, 18.24,







1.46 (d, J = 6.4 Hz,
17.96







3H), 1.32 (q, J = 11.1 HZ,








1H), 1.08 (dd, J = 16.2,








7.7 Hz, 1H)



F107
Off-White
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Solid


(m/z)
8.31 (d, J = 8.0 Hz,
(CDCl3) δ






[M + H]+
1H), 8.27 (d, J = 5.4 Hz,
172.54,






calcd for
1H),
170.28,






C29H36F3N2O9,
7.34-7.20 (m, 2H),
163.01,






613.2367;
7.01-6.88 (m, 4H), 5.74 (s, 2H),
160.28,






found,
4.91 (dq, J = 9.6, 6.4 Hz,
157.36,






613.2398
1H), 4.65 (dt, J = 10.7,
145.73,







7.6 Hz, 1H),
144.01,







4.37 (t, J = 5.5 Hz,
142.30,







1H), 3.91 (s, 3H),
129.59,







3.79 (dt, J = 9.1, 6.1 Hz,
127.15 (q, J = 276.0 Hz),







1H), 3.71 (dt, J = 9.2,
121.38,







5.9 Hz, 1H),
116.32,







3.64 (dd, J = 9.6, 7.3 Hz,
109.65, 89.51,







1H), 2.37 (dt, J = 13.7,
83.68, 82.56,







7.0 Hz, 1H),
72.42, 71.83,







2.26-2.12 (m, 1H),
56.19, 51.56,







2.10-1.89 (m, 5H),
33.24,







1.85-1.61 (m, 4H),
30.69 (q, J = 29.0 Hz),







1.44 (d, J = 6.4 Hz,
28.33,







3H), 1.31 (q, J = 11.1 Hz,
22.93 (q, J = 2.9 Hz),







1H), 1.07 (dd, J = 16.1,
20.87, 18.24,







7.8 Hz, 1H)
17.92


F108
Clear Tacky
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Solid


(m/z)
8.37 (d, J = 8.0 Hz,
(CDCl3) δ






[M + H]+
1H), 8.26 (d, J = 5.4 Hz,
176.25,






calcd for
1H),
172.53,






C31H40F3N2O9,
7.32-7.21 (m, 2H),
162.98,






641.2680;
7.00-6.87 (m, 4H), 5.77 (d, J = 1.5 Hz,
160.26,






found,
2H), 4.91 (dq,
157.36,






641.2686
J = 9.6, 6.4 Hz, 1H),
145.60,







4.65 (dt, J = 10.7, 7.6 Hz,
144.23,







1H), 4.37 (t, J = 5.5 Hz,
141.97,







1H), 3.89 (s,
129.58,







3H), 3.75 (ddt, J = 33.0,
127.15 (q, J = 276.1 Hz),







9.2, 6.0 Hz,
121.38,







2H), 3.64 (dd, J = 9.6,
116.32,







7.3 Hz, 1H),
109.58, 89.87,







2.55 (hept, J = 7.0 Hz,
83.69, 82.56,







1H), 2.36 (dt, J = 13.6,
72.40, 71.83,







7.0 Hz, 1H),
56.14, 51.56,







2.24-2.10 (m, 1H),
33.85, 33.25,







2.02 (ddddt, J = 29.4,
30.69 (q, J = 29.0 Hz),







15.3, 11.0, 7.5, 3.4 Hz,
28.32,







2H),
22.93 (q, J = 2.9 Hz),







1.85-1.62 (m, 4H), 1.44 
18.67,







(d, J = 6.4 Hz, 3H),
18.24, 17.92







1.40-1.24 (m, 1H), 1.14 (d,








J = 7.0 Hz, 6H),








1.07 (dd, J = 16.1, 7.8 Hz,








1H)



F109
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.52 (d, J = 7.6 Hz,
(CDCl3) δ






[M + H]+
1H), 8.32 (d, J = 5.4 Hz,
172.42,






calcd for
1H),
168.89,






C28H34F3N2O8,
7.32-7.22 (m, 2H), 7.00 
162.44,






583.2262;
(d, J = 5.5 Hz, 1H),
159.45,






found,
6.98-6.93 (m, 1H),
157.36,






583.2270
6.91 (dd, J = 8.7, 1.0 Hz,
146.70,







2H), 4.91 (dq, J = 9.6,
141.32,







6.4 Hz, 1H),
137.51,







4.64 (dt, J = 10.7, 7.6 Hz,
129.59,







1H), 4.41-4.33 (m,
127.15 (q, J = 276.0 Hz),







1H), 3.90 (s, 3H),
121.39,







3.74 (ddt, J = 33.5,
116.32,







9.2, 6.0 Hz, 2H),
109.85, 83.67,







3.62 (dd, J = 9.6, 7.2 Hz,
82.56, 72.43,







1H), 2.40 (s, 3H),
71.82, 56.29,







2.35 (dt, J = 13.5, 7.0 Hz,
51.28, 33.46,







1H), 2.16 (dddd,
30.69 (q, J = 28.9 Hz),







J = 15.8, 10.1, 6.2,
28.36,







3.8 Hz, 1H),
22.93 (q, J = 3.0 Hz),







2.10-1.88 (m, 2H),
20.74,







1.82-1.59 (m, 4H), 1.43 (d,
18.20, 17.90







J = 6.4 Hz, 3H),








1.34-1.23 (m, 1H),








1.06 (dd, J = 16.1, 7.7 Hz,








1H)



F110
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.50 (d, J = 7.2 Hz,
(CDCl3) δ






[M + H]+
1H), 8.32 (d, J = 5.4 Hz,
172.42,






calcd for
1H),
169.42,






C30H38F3N2O9,
7.32-7.20 (m, 2H),
162.39,






627.2524;
7.01-6.93 (m, 2H), 6.90 (dd, J = 8.7,
159.45,






found,
1.0 Hz, 2H),
157.36,






627.2539
4.90 (dq, J = 9.6, 6.4 Hz,
146.76,







1H), 4.63 (dt, J = 10.7,
141.35,







7.6 Hz, 1H),
137.36,







4.37 (t, J = 5.4 Hz,
129.59,







1H), 3.89 (s, 3H),
127.15 (q, J = 276.0 Hz),







3.85-3.75 (m, 3H),
121.39,







3.74-3.66 (m, 1H),
116.31,







3.62 (dd, J = 9.6, 7.2 Hz,
109.85, 83.67,







1H), 3.41 (s, 3H),
82.56, 72.42,







2.98 (t, J = 6.6 Hz,
71.82, 67.57,







2H), 2.33 (dt, J = 13.7,
58.78, 56.32,







7.0 Hz, 1H),
51.26, 34.62,







2.23-1.88 (m, 3H),
33.45,







1.81-1.54 (m, 4H),
30.68 (q, J = 28.9 Hz),







1.43 (d, J = 6.4 Hz,
28.34,







3H), 1.37-1.20 (m,
22.92 (q, J = 3.0 Hz),







1H), 1.06 (dd, J = 16.1,
18.21, 17.89







7.7 Hz, 1H)



F111
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
12.06 (s, 1H),
(CDCl3) δ






[M + H]+
8.47 (d, J = 8.1 Hz, 1H),
171.98,






calcd for
7.98 (d, J = 5.2 Hz,
168.70,






C31H37N2O7,
1H), 7.31-7.17 (m,
157.51,






549.2595;
4H), 7.17-7.11 (m,
155.36,






found,
1H), 7.11-7.04 (m,
148.74,






549.2610
2H), 7.00-6.89 (m,
141.91,







3H), 6.86 (d, J = 5.2 Hz,
140.55,







1H), 4.94 (dq, J = 9.6,
130.35,







6.4 Hz, 1H),
129.56,







4.63 (dt, J = 10.7, 7.7 Hz,
128.35,







1H), 4.41 (t, J = 5.5 Hz,
128.27,







1H), 3.93 (s, 3H),
125.71,







3.79 (dt, J = 9.1, 6.3 Hz,
121.33,







1H),
116.57,







3.72-3.62 (m, 2H),
109.51, 83.51,







2.66-2.52 (m, 2H), 2.36 (dt, J = 13.6,
82.81, 73.09,







7.0 Hz, 1H),
72.99, 56.08,







2.26-2.11 (m, 1H),
51.25, 33.20,







1.88-1.75 (m, 3H),
32.32, 31.87,







1.66 (t, J = 6.8 Hz,
28.20, 18.20,







1H), 1.48 (d, J = 6.4 Hz,
18.01







3H), 1.35 (q, J = 11.0 Hz,








1H),








1.06 (dd, J = 16.1, 7.8 Hz,








1H)



F112
Off-White
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Foam


(m/z)
8.37 (d, J = 8.0 Hz,
(CDCl3) δ






[M + H]+
1H), 8.26 (d, J = 5.3 Hz,
176.26,






calcd for
1H),
172.58,






C36H45N2O9,
7.30-7.18 (m, 4H),
162.98,






649.3120;
7.18-7.11 (m, 1H),
160.25,






found,
7.11-7.04 (m, 2H),
157.57,






649.3133
7.01-6.88 (m, 4H),
145.61,







5.81-5.73 (m, 2H), 4.92 (dq, J = 9.6,
144.21,







6.4 Hz, 1H),
142.02,







4.65 (dt, J = 10.7, 7.6 Hz,
141.94,







1H), 4.40 (t, J = 5.5 Hz,
129.54,







1H), 3.88 (s, 3H),
128.34,







3.79 (dt, J = 9.1, 6.3 Hz,
128.26,







1H), 3.66 (ddd, J = 12.6,
125.69,







9.4, 6.7 Hz,
121.27,







2H), 2.62-2.47 (m,
116.57,







3H), 2.36 (dt, J = 13.6,
109.58, 89.88,







7.0 Hz, 1H),
83.57, 82.89,







2.23-2.10 (m, 1H),
73.08, 72.70,







1.88-1.71 (m, 4H),
56.14, 51.58,







1.63 (dq, J = 15.7,
33.86, 33.28,







7.8 Hz, 1H), 1.47 (d,
32.32, 31.88,







J = 6.4 Hz, 3H),
28.28, 18.69,







1.37-1.23 (m, 1H),
18.27, 18.00







1.14 (d, J = 7.0 Hz, 6H),








1.06 (dd, J = 16.1,








7.8 Hz, 1H)



F113
White Solid
—
3369,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2941,
(m/z)
12.04 (s, 1H),
(CDCl3) δ





1745,
[M + H]+
8.47 (d, J = 8.1 Hz, 1H),
171.92,





1650,
calcd for
7.99 (d, J = 5.2 Hz,
168.69,





1529
C30H35N2O7,
1H), 7.08-6.94 (m,
157.54,






535.2439;
6H), 6.87 (d, J = 5.1 Hz,
155.43,






found,
1H), 6.78 (d, J = 8.5 Hz,
155.37,






535.2432
2H), 5.12 (dq,
148.74,







J = 9.6, 6.5 Hz, 1H),
140.55,







4.78-4.52 (m, 2H),
131.00,







4.46 (ddd, J = 7.2,
130.92,







5.3, 1.7 Hz, 1H),
130.32,







3.94 (s, 3H), 2.41 (dt, J = 13.7,
129.89,







7.1 Hz, 1H),
117.08,







2.26 (d, J = 7.0 Hz,
116.46,







7H), 1.91 (q, J = 11.4,
109.50, 82.88,







9.2 Hz, 1H),
82.70, 72.81,







1.76 (dq, J = 15.4,
56.08, 51.24,







7.7 Hz, 1H), 1.43 (d,
33.25, 28.05,







J = 6.5 Hz, 3H),
20.52, 20.50,







1.42-1.38 (m, 1H),
18.27, 18.20







1.19-0.99 (m, 1H)



F114
White Solid
—
3370,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2960,
(m/z)
12.09 (s, 1H),
(CDCl3) δ





2938,
[M + H]+
8.48 (d, J = 8.2 Hz, 1H),
172.04,





2876,
calcd for
7.98 (d, J = 5.2 Hz,
168.65,





1743,
C22H35N2O7,
1H), 6.87 (d, J = 5.2 Hz,
155.34,





1650,
439.2439;
1H), 4.80 (pd, J = 6.3,
148.71,





1529,
found,
2.1 Hz, 1H),
140.52,





1265
439.2461
4.66-4.38 (m, 1H),
130.40,







3.94 (s, 3H), 3.78 (dt, J = 9.0,
109.46, 84.16,







6.5 Hz, 1H),
83.76, 75.50,







3.54 (ddt, J = 30.9, 9.0,
73.30, 70.92,







6.6 Hz, 2H),
56.07, 51.30,







3.43-3.25 (m, 3H),
33.36, 27.90,







2.37 (dddd, J = 13.6, 8.0,
23.53, 23.36,







6.3, 2.0 Hz, 1H),
18.24, 17.91,







2.24-2.06 (m, 1H),
10.78, 10.70







1.75-1.52 (m, 6H),








1.44-1.31 (m, 4H),








0.98-0.81 (m, 7H)



F115
White Solid
—
3377,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2943,
(m/z)
8.32 (d, J = 8.0 Hz,
(CDCl3) δ





1751,
[M + H]+
1H), 8.28 (d, J = 5.3 Hz,
172.54,





1678,
calcd for
1H),
170.31,





1506,
C33H39N2O9,
7.10-6.92 (m, 7H), 6.77 (d, J = 8.6 Hz,
162.99,





1202
607.2650;
2H), 5.74 (s,
160.28,






found,
2H), 5.10 (dq, J = 9.6,
157.59,






607.2672
6.3 Hz, 1H),
155.49,







4.67 (dt, J = 10.7, 7.6 Hz,
145.73,







1H), 4.58 (dd, J = 9.5,
144.05,







7.3 Hz, 1H),
142.30,







4.49-4.40 (m, 1H),
130.94,







3.91 (s, 3H), 2.41 (dt, J = 13.7,
130.86,







7.1 Hz, 1H),
129.87,







2.26 (s, 3H), 2.25 (s,
117.09,







3H), 2.24-2.19 (m,
116.47,







1H), 2.07 (s, 3H),
109.63, 89.54,







1.96-1.83 (m, 1H),
82.98, 82.77,







1.75 (d, J = 8.0 Hz,
72.54, 56.19,







1H), 1.41 (d, J = 6.4 Hz,
51.59, 33.32,







3H),
28.14, 20.89,







1.39-1.24 (m, 1H), 1.13 (dd, J = 16.0,
20.50, 18.35,







7.6 Hz, 1H)
18.20


F116
Colorless
—
3377,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Semi-Solid

2960,
(m/z)
8.32 (d, J = 8.1 Hz,
(CDCl3) δ





2937,
[M + Na]+
1H), 8.27 (d, J = 5.4 Hz,
172.66,





2876,
calcd for
1H), 6.95 (d, J = 5.4 Hz,
170.29,





1745,
C25H38N2NaO9,
1H), 5.74 (s,
162.97,





1676,
533.2470;
2H), 4.79 (ddq, J = 13.6,
160.26,





1503,
found,
6.6, 4.4, 3.2 Hz,
145.75,





1236
533.2488
1H), 4.60 (dt, J = 10.7,
143.97,







7.6 Hz, 1H),
142.41,







3.91 (s, 3H), 3.77 (dt,
109.61, 89.53,







J = 8.9, 6.5 Hz, 1H),
84.24, 83.81,







3.58 (dt, J = 9.0, 6.7 Hz,
75.48, 73.01,







1H), 3.50 (dt, J = 9.0,
70.89, 56.19,







6.6 Hz, 1H),
51.63, 33.43,







3.42-3.22 (m, 3H),
27.96, 23.52,







2.38 (dtd, J = 13.7, 6.7,
23.36, 20.88,







1.7 Hz, 1H),
18.30, 17.90,







2.16-2.08 (m, 1H), 2.07 (s,
10.78, 10.70







3H), 1.73-1.50 (m,








6H), 1.39 (d, J = 6.3 Hz,








3H),








1.36-1.26 (m, 1H),








0.97-0.85 (m, 7H)



F117
Off-White
—
—
HRMS FAB (m/z)
1H NMR (CDCl3)
13CNMR



Amorphous


[M]+
δ 12.08 (s, 1H),
(CDCl3) δ



Solid


calcd for
8.47 (d, J = 8.2 Hz, 1H),
172.0, 168.7,






C24H34N2O7,
7.98 (d, J = 5.1 Hz,
155.3, 148.7,






462.2378;
1H), 6.87 (d, J = 5.2 Hz,
140.5, 130.4,






found,
1H),
109.5, 84.1,






462.2366
4.88-4.78 (m, 1H), 4.59 (dt, J = 10.7,
83.4, 78.7,







7.5 Hz, 1H),
74.0, 73.2,







3.94 (s, 3H),
56.1, 51.3,







3.79-3.60 (m, 2H),
33.3, 28.0,







3.53-3.47 (m, 1H),
18.3, 17.9,







3.47-3.39 (m, 2H),
11.1, 11.0,







3.39-3.24 (m, 2H),
3.1, 3.1, 2.9,







2.42-2.31 (m, 1H),
2.9







2.19-2.06 (m, 1H),








1.76-1.59 (m, 2H), 1.43 (d,








J = 6.4 Hz, 3H),








1.41-1.32 (m, 1H),








1.15-1.00 (m, 2H),








0.98-0.89 (m, 1H),








0.60-0.49 (m, 4H),








0.27-0.16 (m, 4H)



F118
White Solid
119-121
3694,
HRMS-ESI
1H NMR (CDCl3) δ
13CNMR





3369,
(m/z)
12.09 (s, 1H),
(CDCl3) δ





2958,
[M + H]+
8.47 (d, J = 8.2 Hz, 1H),
172.07,





2873,
calcd for
7.99 (d, J = 5.2 Hz,
168.64,





1739,
C24H37N2O7,
1H), 6.86 (d, J = 5.2 Hz,
155.33,





1650,
465.2595;
1H), 4.80 (dq, J = 9.6,
148.70,





1576,
found,
6.4 Hz, 1H),
140.50,





1528
465.2601
4.58 (dt, J = 10.7, 7.7 Hz,
130.39,







1H), 4.07-3.97 (m,
109.45, 83.72,







1H), 3.94 (s, 3H),
81.67, 79.20,







3.78 (dt, J = 8.8, 6.6 Hz,
75.84, 73.46,







1H), 3.55 (dt, J = 8.7,
56.06, 51.31,







6.9 Hz, 1H),
33.53, 33.39,







3.42 (ddd, J = 7.1, 5.1, 1.7 Hz,
31.90, 28.37,







1H), 3.32 (dd, J = 9.5,
23.65, 23.52,







7.4 Hz, 1H),
23.34, 18.47,







2.37 (dtd, J = 13.7, 7.2,
17.85, 10.66







6.5, 1.9 Hz, 1H),








2.09 (dddd, J = 15.5,








10.0, 8.2, 5.0 Hz,








1H), 1.79-1.47 (m,








13H), 1.41 (d, J = 6.4 Hz,








3H), 0.93 (t, J = 7.4 Hz,








3H),








0.90-0.85 (m, 1H)



F119
Colorless
99-100
3368,
ESIMS
1H NMR (CDCl3) δ
13CNMR



Clear Solid

2957,
m/z 479.4
12.09 (s, 1H),
(CDCl3) δ





2871,
([M + H]+);
8.47 (d, J = 8.2 Hz, 1H),
172.07,





1744,
HRMS-ESI
7.98 (d, J = 5.2 Hz,
168.64,





1650,
(m/z)
1H), 6.86 (d, J = 5.2 Hz,
155.33,





1529
[M + H]+
1H), 4.81 (dq, J = 9.5,
148.71,






calcd for
6.4 Hz, 1H),
140.50,






C25H39N2O7,
4.58 (dt, J = 10.8, 7.6 Hz,
130.40,






479.2752;
1H), 4.01 (dtd, J = 7.2,
109.45, 83.71,






found,
3.7, 1.2 Hz, 1H),
81.71, 80.94,






479.2766
3.94 (s, 3H),
79.17, 73.52,







3.65 (dd, J = 8.5, 5.9 Hz,
56.06, 51.31,







1H), 3.44 (ddd, J = 7.2,
33.57, 33.38,







5.3, 1.7 Hz, 1H),
31.89, 29.17,







3.32 (ddd, J = 9.5,
28.37, 23.67,







7.2, 3.1 Hz, 2H),
23.38, 19.60,







2.37 (dtd, J = 13.9, 7.1,
19.40, 18.48,







6.6, 1.8 Hz, 1H),
17.93







2.17-2.05 (m, 1H),








1.90-1.77 (m, 1H),








1.77-1.57 (m, 10H),








1.57-1.46 (m, 2H),








1.40 (d, J = 6.4 Hz,








3H), 0.93 (d, J = 6.6 Hz,








3H), 0.90 (d, J = 6.7 Hz,








3H)



F120
White Solid
43-48
3368,
ESIMS
1H NMR (CDCl3) δ
13CNMR





2946,
m/z 533.3
12.07 (s, 1H),
(CDCl3) δ





2873,
([M + H]+);
8.46 (d, J = 8.1 Hz, 1H),
172.03,





1743,
HRMS-ESI
7.99 (d, J = 5.2 Hz,
168.66,





1650,
(m/z)
1H), 6.87 (d, J = 5.2 Hz,
155.35,





1576,
[M + H]+
1H), 4.80 (dq, J = 9.5,
148.73,





1527
calcd for
6.4 Hz, 1H),
140.52,






C25H36F3N2O7,
4.58 (dt, J = 10.8, 7.6 Hz,
130.36,






533.2469;
1H), 4.04-3.96 (m,
127.20 (q, J = 276.2 Hz),






found,
1H), 3.94 (s, 3H),
109.48, 83.97,






533.2474
3.87 (dt, J = 9.0, 6.0 Hz,
81.53, 79.02,







1H), 3.65 (dt, J = 9.1,
73.11, 72.07,







6.3 Hz, 1H),
56.07, 51.29,







3.46-3.38 (m, 1H),
33.55, 33.35,







3.33 (dd, J = 9.5, 7.3 Hz,
31.87,







1H), 2.37 (dtd, J = 13.7,
30.90 (q, J = 28.9 Hz),







7.0, 6.1, 2.2 Hz,
28.21,







1H), 2.27-2.04 (m,
23.63, 23.35,







3H), 1.82 (dq, J = 8.2,
23.06 (q, J = 2.8 Hz),







6.3 Hz, 2H),
18.44, 17.90







1.77-1.47 (m, 10H),








1.39 (d, J = 6.4 Hz, 4H),








0.91 (ddt, J = 15.6,








6.0, 1.9 Hz, 1H)



F121
Colorless
—
3377,
HRMS-ESI
1H NMR (CDCl3) δ
13CNMR



Oil

2936,
(m/z)
8.31 (d, J = 8.2 Hz,
(CDCl3) δ





2874,
[M + H]+
1H), 8.27 (d, J = 5.5 Hz,
172.69,





1744,
calcd for
1H), 6.95 (d, J = 5.5 Hz,
170.29,





1676,
C27H41N2O9,
1H), 5.74 (s,
162.96,





1501
537.2807;
2H), 4.77 (ddt, J = 12.4,
160.26,






found,
7.5, 3.7 Hz,
145.72,






537.2817
1H), 4.66-4.55 (m,
143.98,







1H), 4.06-3.97 (m,
142.43,







1H), 3.91 (s, 3H),
109.57, 89.56,







3.78 (t, J = 7.6, 7.1 Hz,
83.77, 81.76,







1H), 3.55 (td, J = 8.6,
79.17, 75.83,







8.0, 6.3 Hz, 1H),
73.19, 56.18,







3.47-3.37 (m, 1H),
51.63, 33.53,







3.35 (dd, J = 9.5, 7.7 Hz,
33.50, 31.90,







1H), 2.38 (dt, J = 13.7,
28.44, 23.65,







6.8 Hz, 1H),
23.53, 23.34,







2.07 (s, 3H),
20.87, 18.53,







1.79-1.44 (m, 14H),
17.84, 10.66







1.39 (dd, J = 6.5, 1.5 Hz,








3H), 0.93 (t, J = 7.5 Hz,








3H),








0.89-0.82 (m, 1H)



F122
Colorless
—
3377,
HRMS-ESI
1H NMR (CDCl3) δ
13CNMR



Oil

2954,
(m/z)
8.31 (d, J = 8.1 Hz,
(CDCl3) δ





2871,
[M + H]+
1H), 8.27 (d, J = 5.2 Hz,
172.79,





1745,
calcd for
1H), 6.95 (d, J = 5.4 Hz,
170.38,





1676,
C27H43N2O9,
1H), 5.74 (s,
163.06,





1503
551.2963;
2H), 4.79 (dq, J = 9.2,
160.37,






found,
6.5 Hz, 1H), 4.60 (dt,
145.83,






551.2966
J = 10.7, 7.7 Hz, 1H),
144.08,







4.01 (p, J = 4.2 Hz,
142.52,







1H), 3.91 (s, 3H),
109.69, 89.65,







3.65 (dd, J = 8.4, 6.0 Hz,
83.85, 81.89,







1H), 3.43 (t, J = 6.1 Hz,
81.04, 79.23,







1H),
73.35, 56.28,







3.35-3.28 (m, 2H),
51.74, 33.67,







2.37 (dt, J = 13.6, 6.7 Hz,
33.58, 31.99,







1H), 2.07 (s, 3H),
29.27, 28.53,







1.92-1.75 (m, 2H),
23.77, 23.48,







1.65-1.58 (m, 9H),
20.97, 19.71,







1.55-1.44 (m, 2H),
19.50, 18.65,







1.39 (d, J = 6.4 Hz,
18.03







3H), 0.92 (d, J = 6.7 Hz,








3H), 0.90 (d, J = 6.6 Hz,








3H),








0.89-0.83 (m, 1H)



F123
Colorless
—
3375,
HRMS-ESI
1H NMR (CDCl3) δ
13CNMR



Oil

2957,
(m/z)
8.36 (d, J = 8.1 Hz,
(CDCl3) δ





2920,
[M + H]+
1H), 8.27 (d, J = 5.4 Hz,
176.36,





2851,
calcd for
1H), 6.94 (d, J = 5.5 Hz,
172.80,





1744,
C29H45N2O9,
1H), 5.81-5.72 (m, 2H),
163.05,





1677,
565.3120;
4.78 (dq, J = 10.2, 6.5 Hz,
160.36,





1503
found,
1H), 4.60 (dt, J = 11.1,
145.71,






565.3131
7.5 Hz, 1H),
144.31,







4.06-3.96 (m, 1H),
142.20,







3.88 (s, 3H), 3.78 (dt,
109.64, 90.03,







J = 9.4, 6.6 Hz, 1H),
83.89, 81.88,







3.55 (dt, J = 9.3, 7.0 Hz,
79.28, 75.95,







1H), 3.41 (ddd, J = 7.8,
73.29, 56.25,







5.3, 2.0 Hz,
51.74, 33.97,







1H), 3.32 (dd, J = 9.6,
33.64, 33.62,







7.3 Hz, 1H),
32.02, 28.55,







2.54 (hept, J = 6.7 Hz,
23.77, 23.65,







1H), 2.43-2.31 (m,
23.46, 18.80,







1H), 2.15-2.00 (m,
18.66, 17.96,







1H), 1.81-1.44 (m,
14.24, 10.78







12H), 1.39 (d, J = 6.3 Hz,








2H),








1.36-1.23 (m, 2H), 1.12 (d, J = 8.2 Hz,








6H), 0.92 (t,








J = 7.3 Hz, 3H),








0.90-0.83 (m, 1H)



F124
Colorless
—
3377,
HRMS-ESI
1H NMR (CDCl3) δ
13CNMR



Oil

2954,
(m/z)
8.37 (d, J = 8.1 Hz,
(CDCl3) δ





2972,
[M + H]+
1H), 8.26 (d, J = 5.3 Hz,
176.37,





1744,
calcd for
1H), 6.94 (d, J = 5.4 Hz,
172.81,





1677,
C30H47N2O9,
1H),
163.06,





1502
579.3276;
5.81-5.72 (m, 2H),
160.36,






found,
4.79 (dt, J = 9.7, 6.3 Hz,
145.71,






579.3287
1H), 4.60 (dt, J = 11.1,
144.32,







7.7 Hz, 1H),
142.21,







4.06-3.96 (m, 1H),
109.64, 90.04,







3.88 (s, 3H),
83.88, 81.92,







3.65 (dd, J = 8.5, 6.0 Hz,
81.06, 79.25,







1H), 3.43 (td, J = 5.5,
73.36, 56.25,







2.8 Hz, 1H),
51.76, 33.97,







3.38-3.26 (m, 2H), 2.54 (h,
33.69, 33.61,







J = 7.1 Hz, 1H),
32.01, 29.29,







2.37 (dt, J = 13.6, 6.8 Hz,
28.55, 23.79,







1H),
23.50, 19.73,







2.15-2.01 (m, 1H),
19.53, 18.80,







1.89-1.77 (m, 1H),
18.68, 18.05,







1.77-1.57 (m, 9H),
7.44







1.56-1.47 (m, 1H),








1.39 (d, J = 6.3 Hz,








3H),








1.36-1.29 (m, 1H), 1.14 (d,








J = 7.0, 1.6 Hz, 6H),








0.92 (d, J = 6.7 Hz,








3H), 0.90 (d, J = 6.7 Hz,








3H),








0.88-0.81 (m, 1H)



F125
White Waxy
34-39
3375,
HRMS-ESI
1H NMR (CDCl3) δ
13CNMR



Solid

2953,
(m/z)
8.31 (d, J = 8.1 Hz,
(CDCl3) δ





1749,
[M + H]+
1H), 8.28 (d, J = 5.4 Hz,
172.79,





1677,
calcd for
1H), 6.95 (d, J = 5.4 Hz,
170.42,





1504
C28H40F3N2O9,
1H), 5.74 (s,
163.11,






605.2680;
2H), 4.77 (dq, J = 9.5,
160.41,






found,
6.4 Hz, 1H), 4.60 (dt,
145.86,






605.2688
J = 10.6, 7.6 Hz, 1H),
144.13,







4.00 (ddt, J = 9.1, 5.6,
142.51,







3.4 Hz, 1H), 3.91 (s,
127.35 (d, J = 275.9 Hz),







3H), 3.87 (dt, J = 9.1,
109.74, 89.68,







6.1 Hz, 1H), 3.65 (dt,
84.15, 81.74,







J = 9.0, 6.4 Hz, 1H),
79.12, 72.98,







3.41 (ddd, J = 7.2,
72.19, 56.32,







5.1, 1.8 Hz, 1H),
51.75, 33.67,







3.32 (dd, J = 9.5, 7.4 Hz,
33.57, 32.00,







1H), 2.37 (dt, J = 12.4,
31.04 (d, J = 28.9 Hz),







4.5 Hz, 1H),
28.40, 23.77,







2.26-2.09 (m, 2H),
23.48,







2.07 (s, 3H),
23.20 (d, J = 2.6 Hz),







1.86-1.77 (m, 2H),
21.01,







1.77-1.49 (m, 11H),
18.64, 18.03







1.37 (d, J = 6.3 Hz, 3H),








1.36-1.27 (m, 1H),








0.98-0.81 (m, 1H)



F126
Colorless
—
3386,
HRMS-ESI
1H NMR (CDCl3) δ
13CNMR



Oil

2925,
(m/z)
8.36 (d, J = 8.1 Hz,
(CDCl3) δ





1745,
[M + H]+
1H), 8.27 (d, J = 5.3 Hz,
176.39,





1677,
calcd for
1H), 6.94 (d, J = 5.4 Hz,
172.77,





1503
C30H44F3N2O9,
1H),
163.09,






633.2993;
5.81-5.72 (m, 2H),
160.38,






found,
4.78 (dq, J = 9.5, 6.4 Hz,
145.72,






633.3007
1H), 4.60 (dt, J = 10.7,
144.35,







7.6 Hz, 1H),
142.17,







4.07-3.93 (m, 1H),
127.35 (q, J = 276.1 Hz),







3.89 (s, 3H),
109.67, 90.04,







3.88-3.83 (m, 1H),
84.16, 81.74,







3.65 (dt, J = 9.0, 6.3 Hz,
79.11, 72.96,







1H), 3.41 (ddd, J = 7.0,
72.19, 56.26,







5.1, 1.7 Hz, 1H),
51.75, 33.99,







3.32 (dd, J = 9.5, 7.3 Hz,
33.67, 33.58,







1H), 2.55 (hept, J = 7.1 Hz,
32.00,







1H),
31.04 (q, J = 29.1 Hz),







2.43-2.31 (m, 1H),
29.84,







2.26-2.13 (m, 2H),
28.40, 23.77,







2.13-2.02 (m, 1H),
23.49,







1.87-1.76 (m, 2H),
23.20 (q, J = 3.0 Hz),







1.77-1.46 (m, 10H),
18.81,







1.37 (d, J = 6.2 Hz, 3H),
18.64, 18.03







1.32 (ddd, J = 13.5,








8.1, 2.7 Hz, 1H),








1.14 (d, J = 7.0 Hz, 6H),








0.93-0.81 (m, 1H)



F127
Off-White
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Solid


(m/z)
12.12-12.02 (m,
(CDCl3) δ






[M + H]+
1H), 8.48 (d, J = 8.1 Hz,
171.99,






calcd for
1H), 7.99 (d, J = 5.2 Hz,
168.68,






C25H33N2O7,
1H),
159.70,






473.2282;
7.29-7.25 (m, 2H),
155.36,






found,
7.09 (dd, J = 8.8, 1.0 Hz,
148.74,






473.2278
2H), 7.00-6.92 (m,
140.54,







1H), 6.87 (d, J = 5.2 Hz,
130.36,







1H), 5.03 (dq, J = 9.6,
129.35,







6.4 Hz, 1H),
121.35,







4.62 (dt, J = 10.8, 7.6 Hz,
116.48,







1H), 4.42 (dd, J = 9.6,
109.50, 82.98,







7.3 Hz, 1H),
82.91, 72.86,







3.94 (s, 3H), 3.57 (ddd, J = 7.0,
71.40, 56.08,







5.3, 1.6 Hz,
51.31, 33.37,







1H), 3.45 (dt, J = 9.0,
28.11, 23.16,







6.6 Hz, 1H), 3.25 (dt,
18.32, 18.11,







J = 9.0, 6.5 Hz, 1H),
10.54







2.42 (ddd, J = 13.9,








10.0, 4.4 Hz, 1H)








2.32-2.13 (m, 1H),








1.77 (dq, J = 10.2,








6.5, 5.2 Hz, 2H),








1.50-1.39 (m, 3H),








1.37 (d, J = 6.4 Hz, 3H),








1.06 (dd, J = 16.1,








7.2 Hz, 1H), 0.77 (t, J = 7.4 Hz,








3H)



F128
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
12.06 (d, J = 0.5 Hz,
(CDCl3) δ






[M + H]+
1H), 8.49 (d, J = 8.1 Hz,
171.98,






calcd for
1H), 7.99 (d, J = 5.2 Hz,
168.69,






C31H37N2O7,
1H),
159.66,






549.2595;
7.31-7.20 (m, 4H),
155.37,






found,
7.19-7.07 (m, 3H),
148.75,






549.2602
7.06-7.01 (m, 2H),
142.00,







6.99-6.92 (m, 1H), 6.87 (d,
140.55,







J = 5.2 Hz, 1H),
130.36,







5.04 (dq, J = 9.6, 6.4 Hz,
129.43,







1H), 4.63 (dt, J = 10.8,
128.41,







7.6 Hz, 1H),
128.21,







4.47 (dd, J = 9.6, 7.4 Hz,
125.65,







1H), 3.94 (s, 3H),
121.40,







3.61-3.49 (m, 2H),
116.35,







3.27 (dt, J = 9.2, 6.2 Hz,
109.51, 83.12,







1H),
82.54, 72.86,







2.55-2.46 (m, 2H), 2.42 (dt, J = 13.7,
68.59, 56.09,







6.7 Hz, 1H),
51.30, 33.37,







2.27-2.13 (m, 1H),
32.17, 31.54,







1.88-1.67 (m, 4H),
28.01, 18.31,







1.49-1.39 (m, 1H),
18.10







1.37 (d, J = 6.4 Hz,








3H), 1.05 (dd, J = 16.1,








7.5 Hz, 1H)



F129
White
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Crystalline


(m/z)
12.05 (d, J = 0.5 Hz,
(CDCl3) δ



Solid


[M + H]+
1H), 8.48 (d, J = 8.1 Hz,
171.93,






calcd for
1H), 8.00 (d, J = 5.2 Hz,
168.70,






C26H32F3N2O7,
1H), 7.28 (dd,
159.35,






541.2156;
J = 8.4, 7.0 Hz, 2H),
155.38,






found,
7.04 (dd, J = 8.8, 0.9 Hz,
148.75,






541.2158
2H),
140.55,







7.00-6.93 (m, 1H), 6.87 (d, J = 5.2 Hz,
130.33,







1H), 5.04 (dq,
129.46,







J = 9.6, 6.4 Hz, 1H),
127.18 (q, J = 276.1 Hz),







4.64 (dt, J = 10.8, 7.6 Hz,
121.52,







1H), 4.46 (dd, J = 9.6,
116.03,







7.4 Hz, 1H),
109.52, 83.40,







3.94 (s, 3H), 3.56 (td, J = 6.1,
82.07, 72.69,







5.3, 3.5 Hz, 2H),
67.61, 56.08,







3.28 (dt, J = 9.1, 6.0 Hz,
51.25, 33.29,







1H), 2.42 (dt, J = 13.8,
30.43 (q, J = 28.9 Hz),







6.7 Hz, 1H),
28.00,







2.19 (dddd, J = 15.8,
22.59 (q, J = 2.9 Hz),







10.1, 8.2, 5.3 Hz,
18.25,







1H), 1.96-1.70 (m,
18.02







4H), 1.66-1.58 (m,








2H), 1.50-1.40 (m,








1H), 1.38 (d, J = 6.4 Hz,








3H), 1.08 (dd, J = 16.2,








7.5 Hz, 1H)



F130
Clear Tacky
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Solid


(m/z)
8.31 (d, J = 8.0 Hz,
(CDCl3) δ






[M + H]+
1H), 8.27 (d, J = 5.4 Hz,
172.59,






calcd for
1H),
170.29,






C34H41N2O9,
7.30-7.24 (m, 2H), 7.21 (t, J = 7.2 Hz,
163.01,






621.2807;
2H), 7.14 (dd,
160.27,






found,
J = 8.5, 6.0 Hz, 1H),
157.57,






621.2809
7.08 (d, J = 7.0 Hz,
145.75,







2H), 7.00-6.89 (m,
144.00,







4H), 5.74 (s, 2H),
142.35,







4.92 (dq, J = 9.7, 6.3 Hz,
141.94,







1H), 4.65 (dt, J = 10.7,
129.54,







7.6 Hz, 1H),
128.34,







4.40 (t, J = 5.6 Hz,
128.26,







1H), 3.90 (s, 3H),
125.69,







3.79 (dt, J = 9.1, 6.3 Hz,
121.27,







1H),
116.58,







3.74-3.59 (m, 2H),
109.65, 89.52,







2.63-2.52 (m, 2H), 2.36 (dt, J = 13.7,
83.56, 82.89,







7.0 Hz, 1H),
73.07, 72.71,







2.27-2.10 (m, 1H),
56.20, 51.59,







2.07 (s, 3H),
33.27, 32.32,







1.81 (dd, J = 14.4, 5.6 Hz,
31.88, 28.28,







3H), 1.64 (dt, J = 15.5,
20.89, 18.27,







7.6 Hz, 1H),
18.01







1.46 (d, J = 6.4 Hz,








3H), 1.37-1.23 (m,








1H), 1.06 (dd, J = 16.0,








7.7 Hz, 1H)



F131
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.52 (d, J = 7.4 Hz,
(CDCl3) δ






[M + H]+
1H), 8.32 (d, J = 5.4 Hz,
172.47,






calcd for
1H),
168.90,






C33H39N2O8,
7.30-7.11 (m, 5H),
162.44,






591.2701;
7.10-7.04 (m, 2H),
159.45,






found,
7.00-6.89 (m, 4H), 4.92 (dq, J = 9.7,
157.57,






591.2706
6.3 Hz, 1H),
146.72,







4.64 (dt, J = 10.7, 7.7 Hz,
141.94,







1H), 4.39 (t, J = 5.5 Hz,
141.35,







1H), 3.88 (s, 3H),
137.51,







3.79 (dt, J = 9.1, 6.3 Hz,
129.55,







1H),
128.35,







3.70-3.59 (m, 2H),
128.27,







2.62-2.52 (m, 2H), 2.40 (s, 3H),
125.70,







2.38-2.28 (m, 1H),
121.28,







2.23-2.09 (m, 1H),
116.58,







1.86-1.75 (m, 3H),
109.85, 83.56,







1.61 (dq, J = 15.6,
82.90, 73.07,







7.6 Hz, 1H), 1.45 (d,
72.73, 56.30,







J = 6.4 Hz, 3H),
51.31, 33.50,







1.28 (q, J = 11.1 Hz, 1H),
32.33, 31.89,







1.05 (dd, J = 16.1,
28.31, 20.77,







7.8 Hz, 1H)
18.24, 17.99


F132
Clear Tacky
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Solid


(m/z)
8.50 (d, J = 7.2 Hz,
(CDCl3) δ






[M + H]+
1H), 8.32 (d, J = 5.4 Hz,
172.47,






calcd for
1H),
169.44,






C35H43N2O9,
7.30-7.12 (m, 5H),
162.39,






635.2963;
7.11-7.05 (m, 2H),
159.45,






found,
7.00-6.88 (m, 4H), 4.92 (dq, J = 9.7,
157.57,






635.2977
6.4 Hz, 1H),
146.77,







4.63 (dt, J = 10.6, 7.7 Hz,
141.94,







1H), 4.39 (t, J = 5.5 Hz,
141.39,







1H), 3.88 (s, 3H),
137.36,







3.85-3.74 (m, 3H),
129.54,







3.72-3.57 (m, 2H),
128.35,







3.41 (s, 3H), 2.98 (t,
128.26,







J = 6.6 Hz, 2H),
125.70,







2.61-2.53 (m, 2H),
121.28,







2.33 (dt, J = 13.7, 7.0 Hz,
116.58,







1H), 2.24-2.08 (m,
109.84, 83.56,







1H), 1.83-1.75 (m,
82.90, 73.06,







3H), 1.61 (dq, J = 16.1,
72.70, 67.59,







7.7 Hz, 1H),
58.80, 56.33,







1.45 (d, J = 6.4 Hz,
51.29, 34.64,







3H), 1.35-1.20 (m,
33.49, 32.32,







1H), 1.05 (dd, J = 16.1,
31.88, 28.29,







7.8 Hz, 1H)
18.24, 17.99


F133
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.33 (d, J = 8.0 Hz,
(CDCl3) δ






[M + H]+
1H), 8.28 (d, J = 5.4 Hz,
172.60,






calcd for
1H),
170.30,






C34H41N2O9,
7.32-7.26 (m, 2H), 7.22 (ddd, J = 7.5,
163.00,






621.2807;
6.4, 1.2 Hz,
160.28,






found,
2H), 7.17-7.07 (m,
159.70,






621.2809
3H), 7.06-7.01 (m,
145.74,







2H), 6.99-6.93 (m,
144.03,







2H), 5.74 (s, 2H),
142.36,







5.02 (dq, J = 9.6, 6.4 Hz,
142.03,







1H), 4.65 (dt, J = 10.7,
129.41,







7.6 Hz, 1H),
128.42,







4.46 (dd, J = 9.6, 7.4 Hz,
128.20,







1H), 3.90 (s, 3H),
125.63,







3.61-3.48 (m, 2H),
121.35,







3.26 (dt, J = 9.2, 6.2 Hz,
116.35,







1H),
109.65, 89.53,







2.54-2.47 (m, 2H), 2.43 (dt, J = 13.6,
83.20, 82.60,







6.8 Hz, 1H),
72.59, 68.54,







2.26-2.10 (m, 1H),
56.20, 51.65,







2.07 (s, 3H),
33.43, 32.17,







1.86-1.65 (m, 4H),
31.55, 28.08,







1.45-1.30 (m, 4H),
20.89, 18.38,







1.05 (dd, J = 16.1, 7.6 Hz,
18.10







1H)



F134
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.54 (d, J = 7.4 Hz,
(CDCl3) δ






[M + H]+
1H), 8.33 (d, J = 5.4 Hz,
172.48,






calcd for
1H),
168.91,






C33H39N2O8,
7.30-7.20 (m, 4H),
162.43,






591.2701;
7.17-7.06 (m, 3H),
159.69,






found,
7.06-6.92 (m, 4H), 5.01 (dq, J = 9.6,
159.46,






591.2705
6.4 Hz, 1H),
146.71,







4.64 (dt, J = 10.7, 7.6 Hz,
142.02,







1H), 4.44 (dd, J = 9.6,
141.38,







7.4 Hz, 1H),
137.52,







3.89 (s, 3H),
129.41,







3.61-3.47 (m, 2H), 3.25 (dt, J = 9.2,
128.42,







6.2 Hz, 1H),
128.21,







2.54-2.47 (m, 2H),
125.64,







2.40 (s, 4H),
121.36,







2.25-2.11 (m, 1H),
116.36,







1.80-1.68 (m, 4H),
109.85, 83.20,







1.41-1.29 (m, 4H), 1.04 (dd, J = 16.1,
82.60, 72.61,







7.5 Hz, 1H)
68.55, 56.30,








51.37, 33.66,








32.17, 31.54,








28.09, 20.76,








18.35, 18.08


F135
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.33 (d, J = 8.0 Hz,
(CDCl3) δ






[M + H]+
1H), 8.28 (d, J = 5.4 Hz,
172.54,






calcd for
1H),
170.30,






C29H36F3N2O9,
7.32-7.24 (m, 2H),
163.00,






613.2367;
7.08-7.00 (m, 2H),
160.28,






found,
6.99-6.92 (m, 2H), 5.74 (s, 2H),
159.38,






613.2378
5.02 (dq, J = 9.6, 6.4 Hz,
145.74,







1H), 4.65 (dt, J = 10.7,
144.03,







7.6 Hz, 1H),
142.31,







4.45 (dd, J = 9.6, 7.4 Hz,
129.44,







1H), 3.91 (s, 3H),
127.19 (q, J = 276.1 Hz),







3.57 (dt, J = 10.7, 5.7 Hz,
121.46,







2H), 3.27 (dt, J = 9.2,
116.03,







6.0 Hz, 1H),
109.66, 89.50,







2.43 (dt, J = 13.6, 6.8 Hz,
83.46, 82.12,







1H), 2.26-2.11 (m,
72.41, 67.56,







1H), 2.07 (s, 3H),
56.19, 51.60,







1.87 (dtt, J = 22.6,
33.34,







11.3, 3.2 Hz, 2H),
30.43 (q, J = 28.8 Hz),







1.80-1.67 (m, 2H),
28.05,







1.62 (ddd, J = 14.0,
22.58 (q, J = 2.8 Hz),







7.8, 6.4 Hz, 2H),
20.87,







1.45-1.32 (m, 4H),
18.32, 18.01







1.08 (dd, J = 16.1, 7.6 Hz,








1H)



F136
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.39 (d, J = 8.0 Hz,
(CDCl3) δ






[M + H]+
1H), 8.27 (d, J = 5.4 Hz,
176.25,






calcd for
1H),
172.53,






C31H40F3N2O8,
7.31-7.24 (m, 2H),
162.98,






641.2680;
7.07-7.00 (m, 2H),
160.25,






found,
7.00-6.92 (m, 2H),
159.39,






641.2687
5.80-5.73 (m, 2H), 5.02 (dq, J = 9.6,
145.60,







6.4 Hz, 1H),
144.23,







4.65 (dt, J = 10.7, 7.6 Hz,
141.97,







1H), 4.45 (dd, J = 9.6,
129.43,







7.4 Hz, 1H),
127.19 (q, J = 276.1 Hz),







3.89 (s, 3H), 3.57 (dt, J = 10.8,
121.45,







5.7 Hz, 2H),
116.03,







3.27 (dt, J = 9.1, 6.0 Hz,
109.60, 89.86,







1H), 2.55 (hept, J = 7.0 Hz,
83.47, 82.13,







1H),
72.39, 67.56,







2.42 (dt, J = 13.7, 6.8 Hz,
56.14, 51.59,







1H), 2.27-2.07 (m,
33.85, 33.34,







1H), 1.87 (dddd, J = 22.2,
30.43 (q, J = 28.8 Hz),







11.1, 7.8, 3.1 Hz,
28.04,







2H),
22.58 (q, J = Hz),







1.78-1.57 (m, 4H), 1.36 (d, J = 6.4 Hz,
18.67,







4H), 1.14 (d,
18.32, 18.01







J = 7.0 Hz, 6H),








1.08 (dd, J = 16.2, 7.6 Hz,








1H)



F137
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.54 (d, J = 7.7 Hz,
(CDCl3) δ






[M + H]+
1H), 8.33 (d, J = 5.4 Hz,
172.42,






calcd for
1H),
168.90,






C28H34F3N2O8,
7.32-7.22 (m, 2H),
162.43,






583.2262;
7.05-6.99 (m, 3H),
159.46,






found,
6.99-6.93 (m, 1H), 5.01 (dq, J = 9.6,
159.38,






583.2272
6.4 Hz, 1H),
146.71,







4.64 (dt, J = 10.7, 7.6 Hz,
141.33,







1H), 4.43 (dd, J = 9.6,
137.52,







7.4 Hz, 1H),
129.44,







3.90 (s, 3H), 3.56 (dt, J = 10.7,
127.19 (q, J = 276.1 Hz),







5.7 Hz, 2H),
121.46,







3.26 (dt, J = 9.1, 6.0 Hz,
116.03,







1H), 2.40 (s, 4H),
109.86, 83.46,







2.22-2.10 (m, 1H),
82.11, 72.42,







1.85 (dtdd, J = 22.1,
67.57, 56.29,







11.0, 7.6, 3.1 Hz,
51.32, 33.56,







2H), 1.77-1.56 (m,
30.43 (q, J = 28.8 Hz),







4H), 1.35 (d, J = 6.4 Hz,
28.07,







4H), 1.07 (dd, J = 16.2,
22.57 (q, J = 2.9 Hz),







7.5 Hz, 1H)
20.74,








18.28, 18.00


F138
Clear Tacky
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Solid


(m/z)
8.33 (d, J = 8.0 Hz,
(CDCl3) δ






[M + H]+
1H), 8.28 (d, J = 5.4 Hz,
172.60,






calcd for
1H), 7.27 (t, J = 8.0 Hz,
170.28,






C28H37N2O9,
2H), 7.09 (d,
162.99,






545.2494;
J = 7.9 Hz, 2H),
160.27,






found,
7.00-6.91 (m, 2H),
159.72,






545.2511
5.74 (s, 2H), 5.01 (dq, J = 9.6,
145.73,







6.4 Hz, 1H),
144.01,







4.64 (dt, J = 10.7, 7.6 Hz,
142.35,







1H), 4.41 (dd, J = 9.6,
129.32,







7.3 Hz, 1H),
121.30,







3.91 (s, 3H), 3.56 (t, J = 5.5 Hz,
116.48,







1H), 3.45 (dt,
109.64, 89.52,







J = 9.0, 6.6 Hz, 1H),
83.04, 82.96,







3.24 (dt, J = 9.0, 6.5 Hz,
72.58, 71.36,







1H), 2.42 (dt, J = 13.8,
56.19, 51.65,







6.6 Hz, 1H),
33.42, 28.17,







2.19 (ddd, J = 15.7,
23.15, 20.87,







8.9, 4.5 Hz, 1H),
18.38, 18.10,







2.07 (s, 3H),
10.54







1.82-1.64 (m, 2H),








1.50-1.32 (m, 6H), 1.05 (dd, J = 16.1,








7.3 Hz, 1H),








0.77 (t, J = 7.4 Hz,








3H)



F139
Clear Tacky
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Oil


(m/z)
8.39 (d, J = 8.0 Hz,
(CDCl3) δ






[M + H]+
1H), 8.27 (d, J = 5.4 Hz,
176.24,






calcd for
1H),
172.59,






C30H41N2O9,
7.31-7.22 (m, 2H),
162.96,






573.2807;
7.12-7.05 (m, 2H),
160.25,






found,
7.00-6.91 (m, 2H),
159.73,






573.2819
5.81-5.73 (m, 2H), 5.01 (dq, J = 9.6,
145.59,







6.4 Hz, 1H),
144.22,







4.64 (dt, J = 10.8, 7.6 Hz,
142.01,







1H), 4.42 (dd, J = 9.6,
129.32,







7.3 Hz, 1H),
121.29,







3.88 (s, 3H), 3.56 (ddd, J = 7.0,
116.48,







5.2, 1.5 Hz,
109.58, 89.87,







1H), 3.50-3.41 (m,
83.04, 82.97,







1H), 3.24 (dt, J = 9.0,
72.56, 71.35,







6.5 Hz, 1H),
56.14, 51.64,







2.55 (hept, J = 7.0 Hz,
33.84, 33.42,







1H), 2.42 (dt, J = 13.9,
28.17, 23.15,







6.6 Hz, 1H),
18.67, 18.39,







2.27-2.12 (m, 1H),
18.10, 10.54







1.74 (ddd, J = 15.3,








11.6, 7.7 Hz, 2H),








1.48-1.32 (m, 6H),








1.14 (d, J = 7.0 Hz,








6H), 1.05 (dd, J = 16.1,








7.3 Hz, 1H),








0.77 (t, J = 7.4 Hz,








3H)



F140
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.51 (d, J = 7.1 Hz,
(CDCl3) δ






[M + H]+
1H), 8.33 (d, J = 5.4 Hz,
172.49,






calcd for
1H),
169.43,






C29H39N2O9,
7.31-7.23 (m, 2H),
162.37,






559.2650;
7.10-7.03 (m, 2H), 6.99 (d, J = 5.5 Hz,
159.72,






found,
1H),
159.45,






559.2666
6.98-6.92 (m, 1H),
146.76,







5.01 (dq, J = 9.7, 6.4 Hz,
141.40,







1H), 4.62 (dt, J = 10.7,
137.35,







7.7 Hz, 1H),
129.33,







4.40 (dd, J = 9.6, 7.3 Hz,
121.30,







1H), 3.89 (s, 3H),
116.48,







3.81 (t, J = 6.6 Hz,
109.84, 83.04,







2H), 3.55 (dd, J = 8.9,
82.96, 72.58,







3.5 Hz, 1H),
71.36, 67.56,







3.49-3.35 (m, 4H),
58.77, 56.32,







3.23 (dt, J = 9.0, 6.5 Hz,
51.35, 34.61,







1H), 2.98 (t, J = 6.6 Hz,
33.61, 28.17,







2H), 2.38 (dt, J = 13.8,
23.14, 18.35,







6.4 Hz, 1H),
18.08, 10.53







2.18 (ddt, J = 15.6,








8.5, 5.0 Hz, 1H),








1.71 (dq, J = 18.0, 7.7, 7.0 Hz,








2H),








1.49-1.27 (m, 6H), 1.04 (dd, J = 16.1,








7.2 Hz, 1H),








0.76 (t, J = 7.4 Hz,








3H)



F141
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.54 (d, J = 7.7 Hz,
(CDCl3) δ






[M + H]+
1H), 8.33 (d, J = 5.4 Hz,
172.49,






calcd for
1H),
168.90,






C27H35N2O8,
7.30-7.24 (m, 2H), 7.08 (dd, J = 8.8,
162.41,






515.2388;
1.0 Hz, 2H),
159.72,






found,
7.00 (d, J = 5.5 Hz, 1H),
159.44,






515.2397
6.98-6.92 (m, 1H),
146.71,







5.01 (dq, J = 9.7, 6.4
141.37,







Hz, 1H), 4.63 (dt, J = 10.7,
137.50,







7.5 Hz, 1H),
129.33,







4.40 (dd, J = 9.6, 7.3 Hz,
121.30,







1H), 3.90 (s, 3H),
116.49,







3.55 (ddd, J = 7.0,
109.84, 83.05,







5.2, 1.5 Hz, 1H),
82.96, 72.60,







3.45 (dt, J = 9.0, 6.6 Hz,
71.38, 56.29,







1H), 3.23 (dt, J = 9.0,
51.37, 33.64,







6.5 Hz, 1H), 2.39 (s,
28.19, 23.14,







4H), 2.26-2.12 (m,
20.74, 18.35,







1H), 1.81-1.66 (m,
18.09, 10.53







2H), 1.49-1.29 (m,








6H), 1.04 (dd, J = 16.1,








7.2 Hz, 1H),








0.76 (t, J = 7.4 Hz,








3H)



F142
White Solid
69-72
3364,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2946,
(m/z)
12.06 (s, 1H),
(CDCl3) δ





1733,
[M + H]+
8.44 (d, J = 8.0 Hz, 1H),
173.89,





1649,
calcd for
7.99 (d, J = 5.2 Hz,
172.14,





1527
C25H35N2O8,
1H), 6.87 (d, J = 5.3 Hz,
168.65,






491.2388;
1H), 5.07 (dd, J = 9.8,
155.36,






found,
7.7 Hz, 1H),
148.74,






491.2393
4.98 (dq, J = 9.8, 6.3 Hz,
140.50,







1H), 4.61 (dt, J = 10.7,
130.35,







7.6 Hz, 1H),
109.48, 79.51,







3.96-3.90 (m, 1H),
78.43, 75.63,







3.94 (s, 3H),
71.82, 56.08,







3.45 (ddd, J = 7.5, 5.4, 2.0 Hz,
51.34, 33.32,







1H), 2.40 (dtd, J = 13.4,
33.21, 32.01,







7.1, 1.4 Hz,
28.73, 23.44,







1H), 2.13 (dddd, J = 15.7,
23.15, 18.22,







10.0, 7.8, 5.4 Hz,
17.32, 12.79,







1H),
8.46, 8.42







1.92-1.35 (m, 13H), 1.30 (d, J = 6.2 Hz,








3H),








1.12-1.00 (m, 3H),








0.93-0.84 (m, 2H)



F143
White Solid
124-125
3376,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2950,
(m/z)
12.06 (s, 1H),
(CDCl3) δ





2870,
[M + H]+
8.44 (d, J = 8.0 Hz, 1H),
175.57,





1734,
calcd for
7.99 (d, J = 5.2 Hz,
172.14,





1652,
C27H39N2O8,
1H), 6.87 (d, J = 5.2 Hz,
168.65,





1527
519.2701;
1H), 5.09 (dd, J = 9.7,
155.36,






found,
7.7 Hz, 1H),
148.74,






519.2709
4.97 (dq, J = 9.7, 6.3 Hz,
140.49,







1H), 4.62 (dt, J = 10.7,
130.35,







7.6 Hz, 1H),
109.48, 79.38,







3.94 (s, 3H),
78.55, 75.37,







3.93-3.88 (m, 1H),
71.87, 56.07,







3.46 (ddd, J = 7.5, 5.4, 1.9 Hz,
51.32, 43.98,







1H), 2.74 (p, J = 8.0 Hz,
33.30, 33.27,







1H),
32.08, 30.31,







2.40 (ddd, J = 12.4, 7.5,
29.74, 28.54,







6.1 Hz, 1H),
25.82, 25.73,







2.22-2.07 (m, 1H),
23.49, 23.27,







2.01-1.34 (m, 19H),
18.20, 17.32







1.28 (d, J = 6.3 Hz, 3H),








1.02 (ddt, J = 16.2,








7.9, 2.1 Hz, 1H)



F144
White Solid
39-43
3380,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2953,
(m/z)
8.30 (d, J = 7.9 Hz,
(CDCl3)δ





1735,
[M + H]+
1H), 8.27 (d, J = 5.3 Hz,
173.86,





1678,
calcd for
1H), 6.96 (d, J = 5.4 Hz,
172.72,





1503
C28H39N2O10,
1H), 5.73 (s,
170.27,






563.2599;
2H), 5.06 (dd, J = 9.8,
162.94,






found,
7.7 Hz, 1H), 4.96 (dq,
160.27,






563.2605
J = 9.7, 6.3 Hz, 1H),
145.68,







4.62 (dt, J = 10.8, 7.5 Hz,
144.03,







1H),
142.28,







3.96-3.92 (m, 1H), 3.91 (s, 3H),
109.62, 89.52,







3.44 (ddd, J = 7.6,
79.47, 78.48,







5.4, 2.0 Hz, 1H),
75.71, 71.51,







2.40 (dt, J = 13.4, 6.4 Hz,
56.18, 51.67,







1H), 2.21-2.09 (m,
33.36, 33.18,







1H), 2.07 (s, 3H),
31.99, 29.68,







1.81-1.44 (m, 10H),
28.82, 23.43,







1.36 (dtd, J = 12.9,
23.14, 20.85,







11.2, 1.6 Hz, 1H),
18.30, 17.30,







1.29 (d, J = 6.2 Hz,
12.78, 8.42







3H), 1.09-0.98 (m,








3H), 0.93-0.79 (m,








3H)



F145
White Solid
48-51
3379,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2946,
(m/z)
8.35 (d, J = 8.0 Hz,
(CDCl3) δ





2875,
[M + H]+
1H), 8.27 (d, J = 5.4 Hz,
176.25,





17334,
calcd for
1H), 6.94 (d, J = 5.4 Hz,
173.86,





1676,
C30H43N2O10,
1H),
172.73,





1503
591.2912;
5.80-5.72 (m, 2H),
162.92,






found,
5.06 (dd, J = 9.8, 7.7 Hz,
160.25,






591.2918
1H), 4.96 (dq, J = 9.7,
145.55,







6.2 Hz, 1H),
144.26,







4.62 (dt, J = 10.7, 7.5 Hz,
141.97,







1H), 3.95-3.88 (m,
109.55, 89.90,







1H), 3.89 (s, 3H),
79.47, 78.48,







3.44 (ddd, J = 7.6,
75.72, 71.51,







5.5, 2.0 Hz, 1H),
56.13, 53.44,







2.55 (hept, J = 7.0 Hz,
51.67, 33.83,







1H), 2.40 (dtd, J = 13.4,
33.38, 33.19,







7.2, 1.5 Hz,
32.00, 28.84,







1H), 2.20-2.04 (m,
23.43, 23.14,







1H), 1.81-1.44 (m,
18.66, 18.31,







11H), 1.44-1.31 (m,
17.31, 12.78,







1H), 1.29 (d, J = 6.2 Hz,
8.42, 8.37







3H), 1.14 (d, J = 7.0 Hz,








6H),








1.08-0.97 (m, 3H),








0.92-0.85 (m, 2H)



F146
White Solid
144-145
2955,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





1770,
(m/z)
8.54-8.47 (m, 1H),
(CDCl3) δ





1745,
[M + H]+
8.32 (d, J = 5.4 Hz,
172.56,





1680,
calcd for
1H), 6.99 (d, J = 5.5 Hz,
169.39,





1509
C29H45N2O9,
1H), 4.78 (dq, J = 9.5,
162.31,






565.3120;
6.3 Hz, 1H),
159.41,






found,
4.58 (ddd, J = 10.7, 8.5,
146.72,






565.3124
7.3 Hz, 1H),
141.43,







4.00 (ddt, J = 6.6, 4.2, 2.6 Hz,
137.30,







1H), 3.89 (s, 3H),
109.77, 83.72,







3.81 (t, J = 6.6 Hz,
81.78, 80.91,







2H), 3.65 (dd, J = 8.5,
79.11, 73.22,







5.9 Hz, 1H),
67.56, 58.76,







3.45-3.41 (m, 1H),
56.30, 51.32,







3.40 (s, 3H), 3.30 (dt, J = 9.7,
34.61, 33.66,







7.4 Hz, 2H),
33.55, 31.87,







2.98 (t, J = 6.6 Hz, 2H),
29.15, 28.41,







2.40-2.28 (m, 1H),
23.65, 23.36,







2.07 (dddd, J = 15.7,
19.59, 19.39,







10.0, 8.3, 5.1 Hz,
18.50, 17.90







1H), 1.83 (dt, J = 13.2,








6.7 Hz, 1H),








1.76-1.45 (m, 10H),








1.38 (d, J = 6.4 Hz,








3H), 1.35-1.25 (m,








1H), 0.92 (d, J = 6.6 Hz,








3H), 0.90 (d, J = 6.6 Hz,








3H;








0.90-0.85 (m, 1H)



F147
White Solid
44-47
3379,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2951,
(m/z)
8.52-8.45 (m, 1H),
(CDCl3) δ





1735,
[M + H]+
8.32 (d, J = 5.4 Hz,
173.85,





1679,
calcd for
1H), 7.00 (d, J = 5.5 Hz,
172.61,





1508
C29H41N2O10,
1H), 5.05 (dd, J = 9.8,
169.40,






577.2756;
7.7 Hz, 1H),
162.30,






found,
4.95 (dq, J = 9.8, 6.3 Hz,
159.44,






577.2761
1H), 4.61 (dt, J = 10.6,
146.71,







7.6 Hz, 1H),
141.38,







3.92 (dq, J = 5.1, 2.7,
137.34,







2.1 Hz, 1H), 3.89 (s,
109.82, 79.47,







3H), 3.81 (t, J = 6.5 Hz,
78.48, 75.69,







2H), 3.44 (dq, J = 5.8,
71.51, 67.55,







3.6, 2.8 Hz, 1H),
58.76, 56.31,







3.40 (s, 3H), 2.98 (t, J = 6.6 Hz,
51.34, 34.61,







2H),
33.61, 33.18,







2.42-2.31 (m, 1H),
31.99, 28.82,







2.11 (dddd, J = 15.7, 9.9,
23.43, 23.14,







8.2, 4.1 Hz, 1H),
18.27, 17.28,







1.82-1.42 (m, 10H),
12.77, 8.42,







1.41-1.30 (m, 1H),
8.37







1.27 (d, J = 6.3 Hz, 3H),








1.06-0.97 (m, 3H),








0.91-0.82 (m, 3H)



F148
White Solid
48-51
3371,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2952,
(m/z)
8.30 (d, J = 8.0 Hz,
(CDCl3) δ





2871,
[M + H]+
1H), 8.27 (d, J = 5.3 Hz,
175.52,





1737,
calcd for
1H), 6.96 (d, J = 5.4 Hz,
172.72,





1676,
C30H43N2O10,
1H), 5.74 (s,
170.26,





1504
591.2912;
2H), 5.08 (dd, J = 9.8,
162.94,






found,
7.7 Hz, 1H),
160.27,






591.2936
4.95 (dq, J = 9.7, 6.3 Hz,
145.68,







1H), 4.63 (dt, J = 10.8,
144.05,







7.5 Hz, 1H),
142.28,







3.95-3.85 (m, 1H),
109.62, 89.53,







3.91 (s, 3H),
79.33, 78.60,







3.45 (ddd, J = 7.6, 5.4, 1.9 Hz,
75.44, 71.55,







1H), 2.73 (p, J = 8.0 Hz,
56.18, 51.65,







1H),
43.97, 33.36,







2.46-2.34 (m, 1H),
33.25, 32.06,







2.21-2.09 (m, 1H), 2.07 (s,
30.29, 29.72,







3H), 1.99-1.44 (m,
28.63, 25.80,







18H), 1.43-1.30 (m,
25.74, 23.48,







1H), 1.27 (d, J = 6.4 Hz,
23.26, 20.85,







3H), 1.02 (ddt, J = 16.1,
18.28, 17.31







7.9, 2.3 Hz,








1H)



F149
White Foam
—
3368,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2954,
(m/z)
12.06 (s, 1H),
(CDCl3) δ





2871,
[M + H]+
8.44 (d, J = 8.1 Hz, 1H),
175.59,





1737,
calcd for
7.99 (d, J = 5.1 Hz,
172.12,





1528
C26H39N2O8,
1H), 6.87 (d, J = 5.2 Hz,
168.66,






507.2701;
1H), 5.17 (dd, J = 9.7,
155.37,






found,
7.8 Hz, 1H),
148.75,






507.2717
4.97 (dq, J = 9.7, 6.4 Hz,
140.50,







1H), 4.62 (dt, J = 10.9,
130.36,







7.6 Hz, 1H),
109.48, 81.11,







3.94 (s, 3H),
76.14, 75.26,







3.39 (ddd, J = 7.6, 5.3, 1.9 Hz,
71.77, 56.08,







1H), 3.27 (dd, J = 8.7,
51.28, 43.97,







6.3 Hz, 1H),
33.30, 30.13,







2.98 (dd, J = 8.7, 6.6 Hz,
29.77, 28.69,







1H), 2.74 (p, J = 8.0 Hz,
27.73, 25.82,







1H),
25.72, 19.37,







2.47-2.33 (m, 1H),
19.33, 17.95,







2.26-2.10 (m, 1H),
17.26







1.96-1.64 (m, 9H),








1.64-1.52 (m, 2H), 1.41 (dtd, J = 13.2,








11.6, 1.6 Hz,








1H), 1.29 (d, J = 6.4 Hz,








3H), 1.01 (ddt, J = 16.3, 8.0, 2.0 Hz,








1H), 0.85 (d, J = 6.7 Hz,








6H)



F150
White Foam
—
3379,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2954,
(m/z)
8.30 (d, J = 7.8 Hz,
(CDCl3) δ





2872,
[M + Na]+
1H), 8.27 (d, J = 5.3 Hz,
175.56,





1739,
calcd for
1H), 6.95 (d, J = 5.4 Hz,
172.74,





1503
C29H42N2NaO10,
1H), 5.74 (s,
170.33,






601.2732;
2H), 5.16 (dd, J = 9.8,
162.95,






found,
7.8 Hz, 1H),
160.29,






01.2758
4.95 (dq, J = 9.8, 6.4 Hz,
145.68,







1H), 4.64 (dt, J = 10.8,
144.11,







7.6 Hz, 1H),
142.32,







3.91 (s, 3H),
109.60, 89.59,







3.37 (ddd, J = 7.5, 5.3, 1.9 Hz,
81.19, 76.12,







1H), 3.27 (dd, J = 8.7,
75.36, 71.49,







6.3 Hz, 1H),
56.19, 51.62,







2.97 (dd, J = 8.7, 6.6 Hz,
43.98, 33.39,







1H), 2.73 (p, J = 7.9 Hz,
30.13, 29.76,







1H), 2.41 (dt, J = 13.8,
28.69, 27.84,







7.1 Hz, 1H),
25.82, 25.72,







2.24-2.09 (m, 1H),
20.89, 19.37,







2.08 (s, 3H),
19.34, 18.04,







1.95-1.61 (m, 11H),
17.27







1.42-1.29 (m, 1H), 1.27 (d,








J = 6.4 Hz, 3H),








1.07-0.96 (m, 1H),








0.85 (d, J = 6.7 Hz, 6H)



F151
White Foam
—
3379,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2955,
(m/z)
8.50 (d, J = 8.2 Hz,
(CDCl3) δ





2872,
[M + H]+
1H), 8.33 (d, J = 5.4 Hz,
175.57,





1738
calcd for
1H), 7.00 (d, J = 5.5 Hz,
172.62,






C28H41N2O9,
1H), 5.14 (dd,
168.93,






549.2807;
J = 9.8, 7.8 Hz, 1H),
162.36,






found,
4.99-4.91 (m, 1H),
159.45,






549.2832
4.63 (dt, J = 10.8, 7.7 Hz,
146.66,







1H), 3.91 (s, 3H),
141.39,







3.39-3.35 (m, 1H),
137.52,







3.26 (dd, J = 8.7, 6.2 Hz,
109.80, 81.19,







1H), 2.96 (dd, J = 8.7,
76.13, 75.34,







6.6 Hz, 1H),
71.50, 56.29,







2.77-2.69 (m, 1H),
51.33, 43.98,







2.42-2.35 (m, 1H), 2.40 (s,
33.62, 30.13,







3H), 2.23-2.08 (m,
29.76, 28.68,







1H), 1.97-1.60 (m,
27.86, 25.82,







11H), 1.38-1.27 (m,
25.72, 20.76,







1H), 1.26 (d, J = 6.4 Hz,
19.37, 19.33,







3H), 1.00 (dd, J = 15.7,
18.0, 17.24







7.7 Hz, 1H),








0.85 (dd, J = 6.7, 2.6 Hz,








6H)



F152
White Foam
—
3378,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2954,
(m/z)
8.47 (s, 1H), 8.33 (d,
(CDCl3) δ





2872,
[M + H]+
J = 5.4 Hz, 1H),
175.58,





1738
calcd for
6.99 (d, J = 5.4 Hz, 1H),
172.63,






C30H45N2O10,
5.14 (dd, J = 9.8, 7.8 Hz,
169.47,






593.3069;
1H), 4.94 (dq, J = 9.7,
162.32,






found,
6.3 Hz, 1H),
159.46,






593.3077
4.62 (dt, J = 10.8, 7.7 Hz,
146.71,







1H), 3.90 (s, 3H),
141.42,







3.81 (t, J = 6.6 Hz,
137.38,







2H), 3.41 (s, 3H),
109.79, 81.19,







3.37 (ddd, J = 7.5,
76.12, 75.33,







5.2, 1.9 Hz, 1H),
71.49, 67.57,







3.26 (dd, J = 8.7, 6.3 Hz,
58.80, 56.32,







1H), 3.01-2.94 (m,
51.31, 43.98,







2H), 2.73 (p, J = 7.9 Hz,
34.62, 33.62,







1H), 2.37 (dt, J = 13.6,
30.13, 29.76,







7.0 Hz, 1H),
28.68, 27.83,







2.23-2.06 (m, 1H),
25.82, 25.72,







1.96-1.50 (m, 12H),
19.37, 19.33,







1.39-1.29 (m, 1H),
18.00, 17.23







1.26 (d, J = 6.3 Hz,








3H), 1.05-0.95 (m,








1H), 0.85 (d, J = 6.7 Hz,








6H)



F153
White Foam
—
3368,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2958,
(m/z)
12.09 (s, 1H),
(CDCl3) δ





2874,
[M + H]+
8.48 (d, J = 8.2 Hz, 1H),
172.11,





1742,
calcd for
7.98 (d, J = 5.2 Hz,
168.64,





1529
C24H37N2O7,
1H), 6.86 (d, J = 5.2 Hz,
155.34,






465.2595;
1H), 4.76 (dq, J = 9.6,
148.71,






found,
6.4 Hz, 1H),
140.52,






465.2617
4.58 (ddd, J = 10.8, 8.2,
130.41,







7.3 Hz, 1H), 4.30 (td,
109.45, 84.20,







J = 5.3, 2.8 Hz, 1H),
83.37, 81.33,







3.52-3.41 (m, 2H),
73.54, 70.92,







3.36-3.24 (m, 2H),
56.07, 51.33,







2.37 (dtd, J = 13.5,
33.33, 32.92,







7.0, 6.5, 1.9 Hz, 1H),
32.39, 27.79,







2.14 (dddd, J = 15.8,
23.34, 23.26,







10.1, 8.3, 5.3 Hz,
23.22, 18.27,







1H), 1.86-1.46 (m,
18.11, 10.78







12H), 1.42-1.33 (m,








1H), 1.39 (d, J = 6.4 Hz,








3H), 0.93 (t, J = 7.4 Hz,








3H),








0.94-0.88 (m, 1H)



F154
White Foam
—
3379,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2959,
(m/z)
8.37 (d, J = 8.1 Hz,
(CDCl3) δ





2875,
[M + H]+
1H), 8.27 (d, J = 5.3 Hz,
176.27,





1746,
calcd for
1H), 6.93 (d, J = 5.4 Hz,
172.73,





1504
C29H45N2O9,
1H),
162.93,






565.3120;
5.83-5.69 (m, 2H),
160.25,






found,
4.74 (dq, J = 9.7, 6.5 Hz,
145.59,






565.3134
1H), 4.60 (dt, J = 10.8,
144.21,







7.6 Hz, 1H),
142.11,







4.34-4.24 (m, 1H),
109.51, 89.94,







3.89 (s, 3H),
84.28, 83.36,







3.51-3.41 (m, 2H),
81.40, 73.25,







3.36-3.26 (m, 2H),
70.90, 56.13,







2.55 (hept, J = 7.0 Hz,
51.66, 33.86,







1H), 2.37 (dt, J = 14.0,
33.43, 32.93,







6.8 Hz, 1H),
32.39, 27.88,







2.18-2.04 (m, 1H),
23.34, 23.26,







1.85-1.44 (m, 12H),
23.22, 18.68,







1.38 (d, J = 6.4 Hz,
18.34, 18.10,







3H), 1.37-1.25 (m,
10.78







1H), 1.14 (d, J = 7.0 Hz,








6H), 0.93 (t, J = 7.4 Hz,








3H),








0.93-0.88 (m, 1H)



F155
White Foam
—
3380,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2958
(m/z)
8.32 (d, J = 8.0 Hz,
(CDCl3) δ





2874,
[M + H]+
1H), 8.27 (d, J = 5.3 Hz,
172.74,





1746,
calcd for
1H), 6.94 (d, J = 5.4 Hz,
170.31,





1678
C27H41N2O9,
1H), 5.74 (s,
162.96,






537.2807;
2H), 4.74 (dq, J = 9.6,
160.27,






found,
6.4 Hz, 1H),
145.73,






537.2824
4.60 (dt, J = 10.8, 7.6 Hz,
143.99,







1H), 4.30 (h, J = 3.4 Hz,
142.45,







1H), 3.91 (s, 3H),
109.57, 89.57,







3.53-3.41 (m, 2H),
84.28, 83.36,







3.38-3.24 (m, 2H),
81.39, 73.27,







2.38 (ddd, J = 13.7,
70.90, 56.18,







7.0, 5.3 Hz, 1H),
51.66, 33.42,







2.19-2.09 (m, 1H),
32.93, 32.39,







2.07 (s, 3H),
27.87, 23.34,







1.86-1.44 (m, 12H), 1.38 (d, J = 6.4 Hz,
23.26, 23.21,







3H),
20.89, 18.34,







1.36-1.29 (m, 1H), 0.93 (t,
18.10, 10.78







J = 7.4 Hz, 3H),








0.91-0.79 (m, 1H)



F156
White Foam
—
3367,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2952,
(m/z)
12.04 (s, 1H),
(CDCl3) δ





2871,
[M + H]+
8.50 (d, J = 8.2 Hz, 1H),
175.77,





1732,
calcd for
7.99 (dd, J = 5.2, 1.4 Hz,
171.84,





1530
C27H39N2O8,
1H), 6.87 (d, J = 5.2 Hz,
168.67,






519.2701;
1H),
155.33,






found,
4.94-4.81 (m, 2H),
148.69,






519.2719
4.61 (dt, J = 10.9, 7.6 Hz,
140.57,







1H), 4.15-4.07 (m,
130.34,







1H), 3.58 (dd, J = 9.5,
109.49, 83.35,







7.4 Hz, 1H),
80.01, 77.66,







2.74 (p, J = 8.1 Hz, 1H),
73.39, 56.08,







2.36 (dt, J = 13.8, 7.0 Hz,
51.27, 44.07,







1H),
33.12, 32.91,







2.22-2.07 (m, 1H), 1.94 (m,
32.35, 30.55,







1H), 1.86 (q, J = 7.2 Hz,
29.51, 29.31,







2H),
25.82, 25.77,







1.81-1.46 (m, 15H),
23.13, 23.11,







1.46-1.32 (m, 1H), 1.43 (d, J = 6.4 Hz,
18.41, 18.00







3H), 1.10 (dd,








J = 16.2, 7.2 Hz, 1H)



F157
white foam
—
3380,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2948,
(m/z)
8.40 (d, J = 8.1 Hz,
(CDCl3) δ





2872,
[M + H]+
1H), 8.27 (d, J = 5.4 Hz,
176.25,





1744,
calcd for
1H), 6.94 (d, J = 5.4 Hz,
175.79,





1678
C32H47N2O10,
1H),
172.44,






619.3225;
5.83-5.70 (m, 2H),
162.96,






found,
4.89-4.82 (m, 2H),
160.24,






619.3256
4.62 (dt, J = 10.8, 7.6 Hz,
145.63,







1H), 4.17-4.03 (m,
144.15,







J = 4.1 Hz, 1H),
142.01,







3.89 (s, 3H), 3.58 (dd, J = 9.5,
109.56, 89.87,







7.3 Hz, 1H),
83.33, 80.07,







2.80-2.66 (m, 1H),
77.81, 73.10,







2.54 (hept, J = 7.0 Hz,
56.14, 51.60,







1H), 2.36 (dt, J = 13.8,
44.09, 33.86,







6.8 Hz, 1H),
33.21, 32.91,







2.19-2.05 (m, 1H),
32.36, 30.55,







2.01-1.89 (m, 1H),
29.51, 29.33,







1.86 (td, J = 7.9, 7.5,
25.82, 25.77,







5.8 Hz, 2H),
23.13, 23.11,







1.79-1.46 (m, 14H),
18.68, 18.46,







1.41 (d, J = 6.4 Hz, 3H),
17.99







1.39-1.26 (m, 2H),








1.14 (d, J = 7.0 Hz,








6H), 1.13-1.01 (m,








1H)



F158
white foam
—
3360,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2951,
(m/z)
8.34 (d, J = 8.1 Hz,
(CDCl3) δ





2871,
[M + H]+
1H), 8.27 (d, J = 5.3 Hz,
175.80,





1732,
calcd for
1H), 6.95 (d, J = 5.4 Hz,
172.45,





1677
C30H43N2O10,
1H), 5.74 (s,
170.29,






591.2912;
2H), 4.89-4.82 (m,
162.99,






found,
2H), 4.62 (dt, J = 10.8,
160.25,






591.2941
7.7 Hz, 1H),
145.76,







4.10 (p, J = 4.6 Hz,
143.94,







1H), 3.91 (s, 3H),
142.34,







3.58 (dd, J = 9.5, 7.3 Hz,
109.62, 89.51,







1H),
83.33, 80.07,







2.79-2.67 (m, 1H),
77.79, 73.12,







2.42-2.29 (m, 1H),
56.19, 51.61,







2.19-2.08 (m, 1H), 2.07 (s, 3H),
44.09, 33.19,







1.99-1.89 (m, 1H),
32.91, 32.36,







1.86 (td, J = 8.0, 7.5,
30.55, 29.51,







5.7 Hz, 2H),
29.35, 25.82,







1.80-1.46 (m, 15H),
25.77, 23.13,







1.41 (d, J = 6.4 Hz, 3H),
23.11, 20.89,







1.34 (q, J = 11.5 Hz,
18.46, 17.99







1H), 1.09 (ddt, J = 16.0,








7.2, 2.4 Hz, 1H)



F159
white foam
—
3350,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2951,
(m/z)
8.55 (d, J = 8.1 Hz,
(CDCl3) δ





2871,
[M + H]+
1H), 8.33 (d, J = 5.4 Hz,
175.79,





1731,
calcd for
1H), 7.00 (d, J = 5.4 Hz,
172.32,





1676
C29H41N2O9,
1H),
168.90,






561.2807;
4.92-4.77 (m, 2H),
162.42,






found,
4.61 (ddd, J = 10.8, 8.4,
159.41,






561.2834
7.1 Hz, 1H),
146.72,







4.14-4.01 (m, 1H), 3.91 (s,
141.33,







3H), 3.56 (dd, J = 9.5,
137.47,







7.3 Hz, 1H),
109.82, 83.32,







2.79-2.65 (m, 1H),
80.07, 77.74,







2.40 (s, 3H),
73.12, 56.29,







2.38-2.25 (m, 1H), 2.11 (ddt, J = 16.3,
51.34, 44.08,







10.0, 7.4 Hz
33.39, 32.92,







1H), 2.00-1.89 (m,
32.35, 30.55,







1H), 1.85 (td, J = 7.5,
29.51, 29.39,







5.6 Hz, 2H),
25.82, 25.76,







1.79-1.45 (m, 15H),
23.13, 23.11,







1.40 (d, J = 6.4 Hz, 3H),
20.75, 18.43,







1.37-1.26 (m, 1H),
17.97







1.15-1.02 (m, 1H)



F160
White Foam
—
3370,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2952,
(m/z)
12.05 (d, J = 0.6 Hz,
(CDCl3) δ





1743,
[M + H]+
1H), 8.46 (d, J = 8.1 Hz,
172.00,





1503
calcd for
1H), 7.99 (d, J = 5.2 Hz,
168.68,






C27H34FN2O7,
1H),
155.36,






517.2345;
7.02-6.92 (m, 2H),
148.73,






found,
6.92-6.76 (m, 3H),
140.55,






517.2364
4.87 (dq, J = 9.7, 6.4 Hz,
130.34,







1H), 4.63 (dt, J = 10.8,
117.87,







7.7 Hz, 1H),
117.79,







4.31-4.17 (m, 2H),
116.02,







3.94 (s, 3H),
115.79,







3.72 (dd, J = 9.6, 7.1 Hz,
109.49, 83.97,







1H), 2.37 (dt, J = 13.7,
83.86, 80.93,







6.9 Hz, 1H),
73.28, 56.09,







2.14-2.09 (m, 1H),
51.24, 33.21,







1.89-1.76 (m, 1H),
32.85, 32.47,







1.76-1.50 (m, 9H),
28.07, 23.13,







1.46 (d, J = 6.4 Hz,
23.11, 18.21,







3H), 1.41-1.27 (m,
18.06







1H), 1.09-0.97 (m,








1H)



F161
White Foam
—
3375,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2946,
(m/z)
8.37 (d, J = 8.0 Hz,
(CDCl3) δ





1746,
[M + H]+
1H), 8.26 (d, J = 5.3 Hz,
176.27,





1503
calcd for
1H),
172.61,






C32H42FN2O9,
7.03-6.91 (m, 3H),
162.97,






617.2869;
6.91-6.81 (m, 2H),
160.25,






found,
5.88-5.65 (m, 2H), 4.85 (dq, J = 9.6,
156.31,






617.2887
6.4 Hz, 1H),
153.74,







4.64 (dt, J = 10.8, 7.6 Hz,
153.72,







1H), 4.31-4.18 (m,
145.60,







2H), 3.71 (dd, J = 9.6,
144.22,







7.1 Hz, 1H),
142.00,







2.55 (hept, J = 7.0 Hz,
117.87,







1H), 2.44-2.29 (m,
117.79,







1H), 2.18-2.01 (m,
115.99,







1H), 1.87-1.49 (m,
115.76,







10H), 1.45 (d, J = 6.4 Hz,
109.56, 89.89,







3H),
84.05, 83.84,







1.36-1.25 (m, 1H), 1.14 (d, J = 7.0 Hz,
81.00, 72.98,







6H), 1.02 (dd,
56.14, 51.58,







J = 16.0, 7.6 Hz, 1H)
33.86, 33.29,








32.85, 32.47,








28.15, 23.12,








23.11, 18.68,








18.28, 18.05


F162
White Foam
—
3375,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2952,
(m/z)
8.31 (d, J = 8.0 Hz,
(CDCl3) δ





1749,
[M + H]+
1H), 8.27 (d, J = 5.4 Hz,
172.62,





1503
calcd for
1H),
170.31,






C30H38FN2O9,
7.04-6.92 (m, 3H),
162.99,






589.2556;
6.92-6.82 (m, 2H), 5.74 (s, 2H),
160.27,






found,
4.85 (dq, J = 9.7, 6.4 Hz,
156.31,






589.2572
1H), 4.64 (dt, J = 10.8,
153.73,







7.6 Hz, 1H),
153.71,







4.32-4.18 (m, 2H),
145.74,







3.91 (s, 3H),
144.00,







3.71 (dd, J = 9.6, 7.1 Hz,
142.34,







1H), 2.44-2.30 (m,
117.88,







1H), ),
117.80,







2.15-2.05 (m, 1H), 2.07 (s, 3H),
115.99,







1.87-1.47 (m, 10H),
115.76,







1.45 (d, J = 6.4 Hz,
109.62, 89.52,







3H), 1.36-1.26 (m,
84.05, 83.84,







1H), 1.06-0.95 (m,
80.99, 73.00,







1H)
56.19, 51.58,








33.28, 32.85,








32.47, 28.15,








23.12, 23.11,








20.89, 18.28,








18.05


F163
Colorless
—
3365,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Oil

2939,
(m/z)
12.09 (s, 1H),
(CDCl3) δ





2869,
[M + H]+
8.48 (d, J = 8.1 Hz, 1H),
172.07,





1742,
calcd for
7.98 (d, J = 5.2 Hz,
168.65,





1649,
C30H41N2O7,
1H), 7.33-7.23 (m,
155.35,





1576,
541.2908;
2H), 7.19 (d, J = 7.3 Hz,
148.73,





1527,
found,
3H), 6.86 (d, J = 5.2 Hz,
141.98,





1450
541.2915
1H), 4.81 (dq,
140.51,







J = 9.5, 6.4 Hz, 1H),
130.38,







4.58 (dt, J = 10.7, 7.6 Hz,
128.34,







1H), 3.99 (dq, J = 7.6,
128.32,







3.3, 2.4 Hz, 1H),
125.80,







3.93 (s, 3H), 3.85 (dt,
109.47, 83.89,







J = 8.9, 6.5 Hz, 1H),
81.67, 79.14,







3.63 (dt, J = 8.9, 6.7 Hz,
73.55, 73.37,







1H), 3.43 (ddd, J = 7.1,
56.07, 51.32,







5.2, 1.7 Hz,
33.53, 33.38,







1H), 3.33 (dd, J = 9.5,
32.55, 32.04,







7.3 Hz, 1H),
31.88, 28.35,







2.78-2.59 (m, 2H),
23.64, 23.36,







2.36 (dtd, J = 13.6, 7.1,
18.49, 17.96







6.4, 1.9 Hz, 1H),








2.09 (dddd, J = 15.8, 9.9,








8.3, 5.1 Hz, 1H),








2.02-1.80 (m, 2H),








1.77-1.45 (m, 10H),








1.41 (d, J = 6.3 Hz, 3H),








1.40-1.32 (m, 1H),








0.94-0.87 (m, 1H)



F164
Colorless
—
3367,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Oil

2735,
(m/z)
12.09 (s, 1H),
(CDCl3) δ





2871,
[M + H]+
8.47 (d, J = 8.0 Hz, 1H),
172.07,





1746,
calcd for
7.99 (d, J = 5.2 Hz,
168.64, 155.3,





1650,
C26H41N2O7,
1H), 6.86 (d, J = 5.2 Hz,
148.70,





1522,
493.2908;
1H), 4.79 (dqd, J = 9.0,
140.50,





1487
found,
6.4, 3.3 Hz,
130.39,






493.2921
1H), 4.58 (dt, J = 10.7,
109.45, 83.77,







7.4 Hz, 1H),
81.66, 79.19,







4.01 (dq, J = 6.4, 2.2 Hz,
74.32, 73.45,







1H), 3.94 (s, 3H),
56.06, 51.30,







3.81 (dt, J = 8.8, 6.6 Hz,
33.53, 33.40,







1H),
33.35, 31.91,







3.68-3.54 (m, 1H),
30.07, 28.37,







3.48-3.38 (m, 1H),
23.66, 23.36,







3.38-3.27 (m, 1H), 2.37 (dtd, J = 13.8,
22.60, 18.47,







7.2, 6.6, 2.0 Hz,
17.85, 14.04







1H), 2.09 (dddd,








J = 15.7, 10.1, 8.4,








5.1 Hz, 1H),








1.80-1.46 (m, 11H),








1.40 (d, J = 6.4 Hz, 3H),








1.37-1.29 (m, 4H),








0.96-0.81 (m, 6H)



F165
Colorless
—
3377,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Oil

2941,
(m/z)
8.31 (d, J = 8.1 Hz,
(CDCl3) δ





2868,
[M + H]+
1H), 8.27 (d, J = 5.4 Hz,
172.69,





1744,
calcd for
1H),
170.28,





1676,
C33H45N2O9,
7.33-7.24 (m, 2H), 7.19 (d, J = 7.3 Hz,
162.97,





1499
613.3120;
3H), 6.94 (d,
160.27,






found,
J = 5.4 Hz, 1H),
145.74,






613.3119
5.74 (s, 2H), 4.79 (dq, J = 9.6,
143.98,







6.4 Hz, 1H),
142.41,







4.60 (dt, J = 10.7, 7.5 Hz,
142.00,







1H), 3.99 (dq, J = 5.7,
128.34,







3.6 Hz, 1H),
128.32,







3.90 (s, 3H), 3.85 (dt, J = 9.0,
125.79,







6.4 Hz, 1H),
109.61, 89.54,







3.63 (dt, J = 8.8, 6.7 Hz,
83.93, 81.75,







1H), 3.42 (ddd, J = 7.2,
79.11, 73.53,







5.2, 1.7 Hz, 1H),
73.09, 56.19,







3.32 (dd, J = 9.6, 7.3 Hz,
51.64, 33.51,







1H),
33.47, 32.55,







2.77-2.59 (m, 2H),
32.04, 31.88,







2.43-2.31 (m, 1H),
28.42, 23.63,







2.14-2.07 (m, 1H), 2.07 (s, 3H)
23.35, 20.88,







1.98-1.80 (m, 3H),
18.55, 17.95







1.77-1.43 (m, 9H),








1.40 (d, J = 6.4 Hz,








3H), 1.37-1.27 (m,








1H), 0.94-0.83 (m,








1H)



F166
Colorless
—
3377,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Oil

2974,
(m/z)
8.31 (d, J = 7.9 Hz,
(CDCl3) δ





2934,
[M + H]+
1H), 8.27 (d, J = 5.4 Hz,
172.69,





1744,
calcd for
1H), 6.95 (d J = 5.4 Hz,
170.27,





1677,
C29H45N2O9,
1H), 5.74 (s,
162.96,





1502,
565.3120;
2H), 4.77 (dqd, J = 9.9,
160.26,





1455
found,
6.4, 3.7 Hz, 1H),
145.72,






565.3120
4.60 (dt, J = 10.6, 7.6 Hz,
143.97,







1H), 4.01 (dtd, J = 7.4,
142.43,







3.7, 1.5 Hz,
109.58, 89.55,







1H), 3.91 (s, 3H),
83.82, 81.75,







3.80 (dt, J = 8.8, 6.6 Hz,
79.15, 74.29,







1H), 3.58 (dt, J = 8.7,
73.17, 56.18,







6.8 Hz, 1H),
51.63, 33.52,







3.45-3.38 (m, 1H),
33.49, 31.91,







3.31 (dd, J = 9.6, 7.4 Hz,
30.08, 28.44,







1H), 2.43-2.31 (m,
28.37, 23.65,







1H), 2.14-2.01 (m,
23.36, 22.59,







1H), 2.07 (s, 3H),
20.87, 18.53,







1.81-1.46 (m, 11H),
17.84, 14.03







1.38 (d, J = 6.2 Hz,








3H), 1.33 (dtt, J = 10.5,








4.2, 2.3 Hz,








5H), 0.93-0.84 (m,








5H)



F167
White Foam
—
3366,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2950,
(m/z)
12.07 (d, J = 0.7 Hz,
(CDCl3) δ





1742,
[M + H]+
1H), 8.46 (d, J = 8.2 Hz,
172.02,





1505
calcd for
1H), 7.98 (d, J = 5.2 Hz,
168.67,






C28H37N2O8,
1H),
155.35,






529.2544;
6.96-6.64 (m, 5H),
154.32,






found,
4.86 (dq, J = 9.7, 6.4 Hz,
151.48,






529.2544
1H), 4.62 (dt, J = 10.8,
148.72,







7.7 Hz, 1H),
140.53,







4.30 (tt, J = 5.5, 3.6 Hz,
130.36,







1H), 4.19 (ddd, J = 7.1,
118.14,







5.2, 1.7 Hz,
114.63,







1H), 3.94 (s, 3H),
109.48, 84.40,







3.77 (s, 3H),
83.80, 80.93,







3.72 (dd, J = 9.6, 7.1 Hz,
73.32, 56.08,







1H), 2.37 (dt, J = 13.7,
55.66, 51.25,







7.0 Hz, 1H),
33.26, 32.93,







2.17-2.08 (m, 1H),
32.47, 27.91,







1.90-1.48 (m, 10H),
23.15, 18.23,







1.46 (d, J = 6.5 Hz,
18.09







3H), 1.33 (dt, J = 13.5,








11.4 Hz, 1H),








1.03-0.92 (m, 1H)



F168
White Foam
—
3367,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2946,
(m/z)
12.07 (d, J = 0.7 Hz,
(CDCl3) δ





1742,
[M + H]+
1H), 8.47 (d, J = 8.1 Hz,
172.05,





1528
calcd for
1H), 7.99 (d, J = 5.2 Hz,
168.66,






C25H36F3N2O7,
1H), 6.87 (d,
155.35,






533.2469;
J = 5.2 Hz, 1H),
148.72,






found,
4.76 (dq, J = 9.5, 6.4 Hz,
140.53,






533.2472
1H), 4.64-4.53 (m,
130.38,







1H), 4.24 (td, J = 5.3,
128.62,







2.9 Hz, 1H),
125.87,







3.61-3.52 (m, 1H),
109.47, 84.27,







3.47-3.39 (m, 2H),
83.46, 81.20,







3.35-3.31 (m, 1H),
73.50, 67.14,







2.38 (dt, J = 13.7, 6.8 Hz,
56.08, 51.28,







1H), 2.31-2.03 (m,
33.25, 32.85,







3H), 1.89-1.78 (m,
32.40, 31.29,







2H), 1.75-1.52 (m,
31.00, 30.71,







10H), 1.41-1.33 (m,
30.43, 27.72,







1H), 1.40 (d, J = 6.4 Hz,
23.23, 23.20,







3H), 0.94 (ddt, J = 16.2,
22.88, 22.86,







7.6, 1.9 Hz,
22.83, 22.80,







1H)
18.21, 18.05


F169
White Foam
—
3378,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2947,
(m/z)
8.36 (d, J = 8.0 Hz,
(CDCl3) δ





1745,
[M + H]+
1H), 8.26 (d, J = 5.4 Hz,
176.27,





1504
calcd for
1H), 6.93 (d, J = 5.4 Hz,
172.63,






C33H45N2O10,
1H),
162.96,






629.3069;
6.91-6.85 (m, 2H),
160.25,






found,
6.85-6.77 (m, 2H),
154.27,






629.3075
4.84 (dq, J = 9.6, 6.4 Hz,
151.54,







1H), 4.64 (dt, J = 10.8,
145.60,







7.6 Hz, 1H),
144.21,







4.30 (tt, J = 5.5, 3.7 Hz,
142.03,







1H), 4.18 (ddd, J = 7.1,
118.15,







5.2, 1.7 Hz,
114.61,







1H), 3.89 (s, 3H),
109.54, 89.90,







3.77 (s, 3H),
84.49, 83.78,







3.71 (dd, J = 9.6, 7.1 Hz,
81.00, 73.02,







1H), 2.55 (hept, J = 7.0 Hz,
56.13, 55.66,







1H), 2.37 (dt,
51.58, 33.86,







J = 13.7, 7.0 Hz, 1H),
33.35, 32.93,







2.17-2.06 (m, 1H),
32.47, 27.99,







1.87-1.47 (m, 10H),
23.14, 18.68,







1.44 (d, J = 6.4 Hz,
18.30, 18.08







3H), 1.35-1.23 (m,








1H), 1.14 (d, J = 7.0 Hz,








6H),








1.03-0.89 (m, 1H)



F170
White Foam
—
3379,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2949,
(m/z)
8.31 (d, J = 8.1 Hz,
(CDCl3) δ





1748,
[M + H]+
1H), 8.27 (d, J = 5.3 Hz,
172.64,





1677,
calcd for
1H), 6.94 (d, J = 5.4 Hz,
170.31,





1504
C31H41N2O10,
1H),
162.98,






601.2756;
6.92-6.85 (m, 2H),
160.26,






found,
6.85-6.77 (m, 2H), 5.74 (s,
154.28,






601.2763
2H), 4.84 (dq, J = 9.6,
151.54,







6.4 Hz, 1H),
145.73,







4.64 (dt, J = 10.8, 7.6 Hz,
144.00,







1H), 4.30 (tt, J = 5.5,
142.37,







3.7 Hz, 1H),
118.15,







4.18 (ddd, J = 7.0, 5.2, 1.7 Hz,
114.61,







1H), 3.91 (s, 3H),
109.60, 89.54,







3.77 (s, 3H),
84.49, 83.79,







3.71 (dd, J = 9.6, 7.1 Hz,
80.99, 73.04,







1H), 2.37 (dt, J = 13.6,
56.19, 55.66,







7.0 Hz, 1H),
51.59, 33.35,







2.12 (ddd, J = 10.7,
32.93, 32.47,







8.2, 5.4 Hz, 1H),
27.99, 23.14,







2.07 (s, 3H),
20.89, 18.30,







1.89-1.47 (m, 10H), 1.44 (d, J = 6.4 Hz,
18.08







3H),








1.35-1.21 (m, 1H),








0.97 (dd, J = 16.1, 7.8 Hz,








1H)



F171
Colorless
—
3380,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Oil

2946,
(m/z)
8.37 (d, J = 8.0 Hz,
(CDCl3) δ





2876,
[M + H]+
1H), 8.27 (d, J = 5.4 Hz,
176.27,





1745,
calcd for
1H), 6.93 (d, J = 5.4 Hz,
172.66,





1676
C30H44F3N2O9,
1H),
162.95,






633.2993;
5.81-5.71 (m, 2H),
160.24,






found,
4.74 (dq, J = 9.5, 6.4 Hz,
145.60,






633.3010
1H), 4.60 (dt, J = 10.8,
144.21,







7.5 Hz, 1H),
142.06,







4.28-4.20 (m, 1H),
128.63,







3.89 (s, 3H),
125.89,







3.60-3.51 (m, 1H),
109.54, 89.90,







3.46-3.38 (m, 2H),
84.34, 83.43,







3.32 (ddd, J = 7.1, 5.3, 1.6 Hz,
81.26, 73.21,







1H), 2.55 (hept, J = 7.0 Hz,
67.13, 56.14,







1H),
51.62, 33.86,







2.38 (dt, J = 13.7, 6.8 Hz,
33.34, 32.86,







1H), 2.30-2.01 (m,
32.40, 31.01,







3H), 1.92-1.48 (m,
30.73, 27.81,







12H), 1.39 (d, J = 6.4 Hz,
23.23, 23.20,







3H),
22.86, 22.83,







1.36-1.30 (m, 1H), 1.14 (d, J = 7.0 Hz,
18.68, 18.28,







6H),
18.04







0.94 (ddt, J = 16.2, 7.7,








2.1 Hz, 1H)



F172
Colorless
—
3381,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Oil

2949,
(m/z)
8.32 (d, J = 8.0 Hz,
(CDCl3) δ





2874,
[M + H]+
1H), 8.27 (d, J = 5.3 Hz,
172.67,





1747,
calcd for
1H), 6.95 (d, J = 5.4 Hz,
170.31,





1677
C28H40F3N2O9,
1H), 5.74 (s,
162.98,






605.2680;
2H), 4.74 (dq, J = 9.5,
160.26,






found,
6.4 Hz, 1H),
145.74,






605.2686
4.66-4.54 (m, 1H),
143.99,







4.24 (td, J = 5.2, 3.4 Hz,
142.40,







1H), 3.91 (s, 3H),
128.63,







3.61-3.51 (m, 1H),
125.89,







3.47-3.39 (m, 2H),
109.60, 89.54,







3.32 (ddd, J = 7.1,
84.33, 83.44,







5.4, 1.7 Hz, 1H),
81.26, 73.23,







2.38 (dt, J = 13.7, 6.9 Hz,
67.13, 56.19,







1H), 2.31-2.08 (m,
51.62, 33.33,







3H), 2.07 (s, 3H),
32.86, 32.40,







1.92-1.46 (m, 12H),
31.30, 31.01,







1.39 (d, J = 6.4 Hz,
30.73, 30.44,







3H), 1.33 (dt, J = 11.0,
27.81, 23.23,







1.8 Hz, 1H),
23.20, 22.89,







0.93 (ddt, J = 16.1,
22.86, 22.83,







7.6, 1.8 Hz, 1H)
22.80, 20.89,








18.28, 18.04


F173
Colorless
—
3379,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Oil

2949,
(m/z)
8.53 (d, J = 8.4 Hz,
(CDCl3) δ





1772,
[M + H]+
1H), 8.33 (d, J = 5.4 Hz,
172.55,





1743,
calcd for
1H), 7.00 (d, J = 5.5 Hz,
168.92,





1678
C27H38F3N2O8,
1H), 4.73 (dq,
162.40,






575.2575;
J = 9.6, 6.4 Hz, 1H),
159.43,






found,
4.59 (ddd, J = 10.8,
146.70,






575.2588
8.4, 7.2 Hz, 1H),
141.40,







4.26-4.22 (m, 1H),
137.49,







3.91 (s, 3H),
128.62,







3.61-3.50 (m, 1H),
125.88,







3.45-3.39 (m, 2H), 3.32 (ddd, J = 7.1,
109.80, 84.33,







5.3, 1.6 Hz,
83.43, 81.26,







1H), 2.40 (s, 3H),
73.24, 67.14,







2.41-2.33 (m, 1H),
56.29, 51.35,







2.30-2.02 (m, 3H),
33.53, 32.87,







1.91-1.47 (m, 12H),
32.40, 31.30,







1.37 (d, J = 6.4 Hz,
31.01, 30.72,







3H), 1.36-1.27 (m,
30.44, 27.84,







1H), 0.93 (ddt, J = 16.0,
23.23, 23.19,







7.5, 2.0 Hz, 1H)
22.88, 22.85,








22.82, 22.79,








20.75, 18.23,








18.02


F174
Off-White
—
—
ESIMS
—
—



Solid


m/z 328.3








([M + H]+)




F175
White Solid
—
2959,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2936,
(m/z)
8.69 (br s, 3H),
(CDCl3) δ





2878,
[M + H]+
4.74 (t, J = 7.2 Hz, 1H),
169.99, 83.91,





1751,
calcd for
4.01-3.97 (m, 1H),
83.53, 75.52,





1207
C15H30NO4,
3.75 (dt, J = 8.9, 6.5 Hz,
74.21, 70.90,






288.2169;
1H), 3.51 (ddt, J = 29.8,
52.10, 31.28,






found,
9.0, 6.6 Hz,
27.87, 23.49,






288.2167
2H), 3.35-3.15 (m,
23.33, 17.81,







3H), 2.56-2.45 (m,
17.77, 10.76,







1H), 2.11 (s, 1H),
10.67







1.75-1.47 (m, 7H),








1.39 (d, J = 6.2 Hz,








3H), 0.92 (td, J = 7.4,








1.8 Hz, 6H),








0.86-0.71 (m, 1H)



F176
White Solid
226-229
2958,
HRMS-ESI
1H NMR (400 MHz,
13 C NMR (101 MHz,





2873,
(m/z)
(CD3OD) δ 4.78 (pd, J = 6.3,
(CD3OD) δ





2110,
[M + Na]+
2.1 Hz, 1H),
169.68, 83.82,





1743,
calcd for
3.93 (dd, J = 10.7,
83.37, 75.79,





1455,
C16H31NNaO4,
7.4 Hz, 1H), 3.78 (dt,
75.26, 74.00,





1226
324.2145;
J = 8.9, 6.5 Hz, 1H),
51.45, 30.62,






found,
3.58 (dt, J = 8.8, 6.6 Hz,
28.75, 27.26,






324.2156
1H),
23.24, 18.86,







3.38-3.33 (m, 3H), 3.15 (dd, J = 8.7,
18.80, 17.50,







6.2 Hz, 1H),
17.17, 10.02







2.33-2.13 (m, 2H),








1.81 (dp, J = 13.3, 6.7 Hz,








1H), 1.68 (tt, J = 9.8,








4.7 Hz, 2H),








1.62-1.52 (m, 2H),








1.51-1.42 (m, 1H), 1.41 (d,








J = 6.3 Hz, 3H),








0.98-0.86 (m, 9H),








0.84 (dt, J = 16.9, 5.0 Hz,








1H)



F177
White
—
3349,
HRMS-ESI
1H NMR (CDCl3) δ
13 C NMR



Foamy Solid

1635,
(m/z)
8.70 (bs, 3H),
(CDCl3) δ





1502,
[M + H]+
6.99-6.82 (m, 6H),
170.06,





1203
calcd for
6.79-6.68 (m, 2H),
157.87 (d, J = 240.2 Hz),






C21H23F2NO4,
5.10-4.97 (m, 1H),
155.46 (d, J = 2.0 Hz),






392.1668;
4.48-4.40 (m, 1H),
154.48 (d, J = 199.0 Hz),






found,
4.39-4.32 (m, 1H),
153.49 (d, J = 2.0 Hz),






392.1664
4.26-4.09 (m, 1H),
118.13 (d, J = 8.0 Hz),







2.67-2.47 (m, 1H),
117.72 (d, J = 8.1 Hz),







2.29-2.11 (m, 1H),
116.14 (d, J = 4.9 Hz),







1.92-1.66 (m, 3H), 1.37 (d,
115.92 (d, J = 4.6 Hz),







J = 5.9 Hz, 3H),
83.27, 83.09,







1.18-1.04 (m, 1H)
73.33, 52.43,








30.95, 28.65,








18.17, 18.06


F178
White Solid
—
—
ESIMS
1H NMR (CDCl3) δ
19 F NMR






m/z 354.2
8.71 (bs, 3H),
(CDCl3) δ −122.97






([M + H]+)
7.04-6.87 (m, 4H),








5.01-4.89 (m, 1H),








4.25 (dd, J = 9.5, 7.2 Hz,








1H), 4.16-4.03 (m,








1H), 3.54-3.46 (m,








1H), 3.22 (dd, J = 8.7,








6.5 Hz, 1H),








3.02 (dd, J = 8.7, 6.1 Hz,








1H), 2.63-2.51 (m,








1H), 2.29-2.10 (m,








1H), 1.89-1.72 (m,








1H), 1.74-1.59 (m,








3H), 1.33 (d, J = 6.3 Hz,








3H),








1.02-0.90 (m, 1H), 0.79 (d, J = 6.7 Hz,








3H), 0.74 (d,








J = 6.7 Hz, 3H)



F179
White Solid
—
—
ESIMS
1H NMR (CDCl3)
19 F NMR






m/z 354.2
δ 8.64 (bs, 3H),
(CDCl3) δ −122.79






([M + H]+)
7.30-7.23 (m, 1H),








7.22-7.13 (m, 1H),








6.98-6.90 (m, 1H),








6.87-6.80 (m, 1H),








4.87-4.76 (m, 1H),








4.27-4.17 (m, 1H),








4.16-4.01 (m, 1H),








3.57-3.47 (m, 2H),








3.36 (dd, J = 8.7, 6.5 Hz,








1H), 2.89 (t, J = 7.6 Hz,








1H), 2.71 (t, J = 7.6 Hz,








1H),








2.59-2.39 (m, 1H),








2.18-1.99 (m, 1H),








1.80-1.56 (m, 3H), 1.42 (d,








J = 6.0 Hz, 3H),








0.83 (d, J = 6.6 Hz, 3H),








0.79 (d, J = 6.7 Hz,








3H)



F180
White Solid
236-240
2957,
HRMS-ESI
1H NMR (CD3OD) δ
13 C NMR





2878,
(m/z)
6.50 (dtd, J = 15.7,
(CD3OD) δ





1742,
[M + Na]+
4.0, 2.0 Hz, 1H),
170.03,





1458,
calcd for
5.98 (dqt, J = 15.5, 6.6,
137.51,





1108
C17H28F3NNaO4,
2.1 Hz, 1H),
117.43,






390.1863;
4.48 (ddt, J = 15.7, 6.6,
117.09, 83.80,






found,
3.2 Hz, 1H),
83.59, 75.48,






390.1874
4.41-4.29 (m, 1H),
73.41, 70.70,







3.93 (dd, J = 10.7, 7.4 Hz,
51.45, 30.77,







1H), 3.55-3.40 (m,
28.68, 27.05,







2H), 3.37-3.32 (m,
18.45, 18.34,







2H), 3.14 (dd, J = 8.7,
17.37, 16.72;







6.0 Hz, 1H),
19 F NMR







2.24 (dtd, J = 18.3, 9.1,
(CD3OD) δ







4.6 Hz, 2H), 1.80 (dp,
−65.82 (dt, J = 8.4,







J = 13.2, 6.7 Hz, 1H),
2.5 Hz)







1.69 (tt, J = 9.8, 4.5 Hz,








2H),








1.57-1.44 (m, 1H), 1.42 (d, J = 6.4 Hz,








3H), 0.91 (dd,








J = 6.7, 4.4 Hz, 6H),








0.86 (t, J = 4.7 Hz,








1H)



F181
White Solid
—
2933,
HRMS-ESI
1H NMR (CD3OD) δ
13 C NMR





2859,
(m/z)
4.78 (pd, J = 6.3, 2.0 Hz,
(CD3OD) δ





1743,
[M + H]+
1H), 3.93 (dd, J = 10.8,
169.83, 83.87,





1456
calcd for
7.4 Hz, 1H),
83.43, 75.59,






C18H36NO4,
3.80 (dt, J = 8.9, 6.5 Hz,
73.84, 73.39,






330.2639;
1H), 3.62 (dt, J = 8.9,
51.40, 30.57,






found,
6.6 Hz, 1H),
29.73, 28.75,






330.2643
3.39-3.32 (m, 2H),
28.19, 27.18,







3.15 (dd, J = 8.7, 6.1 Hz,
22.19, 18.50,







1H), 2.31-2.14 (m
18.43, 17.41,







2H), 1.81 (dp, J = 13.2,
16.77, 12.98







6.6 Hz, 1H),








1.68 (tt, J = 9.8, 4.6 Hz,








2H),








1.62-1.49 (m, 2H),








1.48-1.38 (m, 2H), 1.41 (d, J = 6.4 Hz,








3H),








1.40-1.28 (m, 4H),








0.97-0.86 (m, 9H),








0.87-0.79 (m, 1H)



F182
Colorless
—
—
ESIMS
1H NMR (CDCl3)
13 C NMR



Solid


m/z 416.3
δ 8.65 (bs, 3H),
(CDCl3) δ






([M + H]+)
7.04-6.92 (m, 2H),
170.03,







6.83-6.66 (m, 6H),
154.57,







5.11-4.92 (m, 1H),
154.46,







4.46-4.36 (m, 1H),
153.68,







4.36-4.25 (m, 1H),
151.51,







4.23-4.07 (m, 1H),
118.44,







3.73 (s, 3H), 3.71 (s, 3H),
117.74,







2.68-2.47 (m, 1H),
114.59,







2.31-2.11 (m, 1H),
114.52, 83.69,







1.90-1.65 (m, 3H),
83.42, 73.48,







1.38 (d, J = 6.2 Hz,
55.61, 52.33,







3H), 1.13-0.95 (m,
30.93, 28.23,







1H)
18.17, 17.94


F183
White Solid
198-200
—
—
1H NMR (CDCl3)δ
13 C NMR







8.64 (bs, 3H),
(CDCl3) δ







6.92-6.71 (m, 4H),
170.03,







4.90-4.72 (m, 1H),
154.32,







4.24-4.15 (m, 1H),
151.36,







4.15-4.02 (m, 1H), 3.76 (s,
118.02,







3H), 3.62-3.49 (m,
114.64, 84.25,







2H), 3.37 (dd, J = 8.7,
83.13, 80.78,







6.6 Hz, 1H),
73.79, 55.65,







2.57-2.41 (m, 1H),
52.21, 30.86,







2.20-2.02 (m, 1H),
29.03, 28.04,







1.84-1.54 (m, 4H),
19.43, 19.33,







1.43 (d, J = 6.2 Hz, 3H),
17.89, 17.78







0.96-0.85 (m, 1H),








0.85 (d, J = 6.7 Hz,








3H), 0.82 (d, J = 6.7 Hz,








3H)



F184
White Solid
246-248
3432,
HRMS-ESI
1H NMR (CDCl3)
13 C NMR





2957,
(m/z)
δ 8.68 (bs, 3H),
(CDCl3) δ





1750
[M + H]+
4.67 (dq, J = 11.2, 5.1, 3.8 Hz,
170.18, 83.36,






calcd for
1H),
81.60, 80.77,






C19H33NO4,
4.35-4.26 (m, 1H),
78.96, 74.53,






340.2482;
4.06-3.93 (m, 2H),
52.20, 33.54,






found,
3.41-3.30 (m, 2H),
32.75, 32.43,






340.2485
2.60-2.42 (m, 1H),
31.70, 31.07,







2.18-2.00 (m, 1H),
28.20, 23.72,







1.86-1.43 (m, 19H), 1.37 (d, J = 6.3 Hz,
23.40, 23.32,







3H),
23.29, 18.06,







0.89-0.74 (m, 1H)
18.01


F185
White Solid
195-197
3389,
HRMS-ESI
1H NMR (CDCl3)δ
13 C NMR





2925,
(m/z)
8.73 (bs, 3H),
(CDCl3) δ





1749,
[M + H]+
7.31-7.21 (m, 2H),
170.07,





1588,
calcd for
7.06-6.99 (m, 2H),
159.61,





1492,
C20H29NO4,
6.98-6.91 (m, 1H),
129.30,





1223
348.2169;
5.04-4.90 (m, 1H),
121.29,






found,
4.33 (dd, J = 9.5, 7.3 Hz,
116.19, 82.30,






348.2181
1H), 4.14-4.01 (m,
80.25, 79.73,







1H), 3.95-3.89 (m,
73.83, 52.21,







1H), 3.62-3.55 (m,
33.35, 31.72,







1H), 2.64-2.46 (m,
31.13, 28.43,







1H), 2.26-2.09 (m,
23.38, 22.94,







1H), 2.08-1.37 (m,
18.08, 18.03







11H), 1.33 (d, J = 6.3 Hz,








3H),








1.03-0.89 (m, 1H)



F186
White Solid
243-245
3367,
HRMS-ESI
1H NMR (CDCl3)δ
—





2954,
(m/z)
8.64 (bs, 3H),






1750,
[M + H]+
7.29-7.21 (m, 2H),






1597,
calcd for
6.97-6.85 (m, 3H),






1493,
C20H29NO4,
4.87-4.73 (m, 1H),






1236
348.2169;
4.33-4.26 (m, 1H),







found,
4.26-4.19 (m, 1H),







348.2137
4.12-3.98 (m, 1H),








3.73-3.61 (m, 2H),








2.58-2.41 (m, 1H),








2.23-2.04 (m, 1H),








1.90-1.45 (m, 10H),








1.42 (d, J = 6.4 Hz, 3H),








0.92 (dd, J = 15.8,








7.2 Hz, 1H)



F187
White Solid
—
2945,
HRMS-ESI
1H NMR (CD3OD) δ
13 C NMR





2888,
(m/z)
4.86-4.74 (m, 1H),
(CD3OD) δ





2109,
[M + H]+
3.95 (dd, J = 10.7,
169.74, 83.68,





1741,
calcd for
7.4 Hz, 1H), 3.82 (dt,
83.52, 73.67,





1251,
C17H28F6NO4,
J = 9.3, 6.1 Hz, 1H),
71.42, 66.57,





1142
424.1917;
3.72 (dt, J = 9.3, 6.2 Hz,
51.36, 30.49,






found,
1H), 3.64 (dt, J = 9.3,
30.29, 30.00,






424.1917
6.3 Hz, 1H),
27.01, 22.65







3.46-3.37 (m, 3H),
(dd, J = 17.9,







2.34-2.15 (m, 5H),
3.2 Hz),







1.87-1.74 (m, 4H),
17.25, 16.76;







1.73-1.62 (m, 2H),
19 F NMR







1.52-1.33 (m, 2H),
(CD3OD) δ







1.42 (d, J = 6.4 Hz, 3H),
−68.04 (q, J = 11.4 Hz)







0.87 (dt, J = 15.3, 4.6 Hz,








1H)



F188
White Solid
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13 C NMR






(m/z)
8.65 (s, 3H),
(CDCl3) δ






[M + H]+
7.32-7.14 (m, 2H),
170.04,






calcd for
7.00-6.82 (m, 3H),
157.52,






C18H28NO4,
4.89-4.77 (m, 1H),
129.50,






322.2013;
4.38-4.29 (m, 1H), 4.10 (t,
121.28,






found,
J = 8.5 Hz, 1H),
116.50, 83.15,






322.2012
3.76-3.64 (m, 1H),
82.81, 75.59,







3.56 (ddd, J = 12.4, 9.3,
73.74, 52.19,







6.8 Hz, 2H), 2.50 (t, J = 12.8 Hz,
30.81, 28.23,







1H),
23.40, 17.81,







2.26-2.03 (m, 1H),
17.77, 10.58







1.69 (tt, J = 16.1, 9.9 Hz,








3H), 1.48 (qd, J = 6.8,








2.4 Hz, 2H),








1.42 (d, J = 6.3 Hz, 3H),








0.96 (dd, J = 15.9,








6.8 Hz, 1H), 0.81 (t, J = 7.4 Hz,








3H)



F189
White Solid
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.63 (s, 3H),
(CDCl3) δ






[M + H]+
7.28-7.19 (m, 2H),
170.05,






calcd for
7.03-6.77 (m, 3H),
157.51,






C20H32NO4,
4.83 (dd, J = 9.6, 6.3 Hz,
129.49,






350.2326;
1H), 4.34 (dt, J = 10.9,
121.26,






found,
5.4 Hz, 1H),
116.46, 83.18,






350.2319
4.09 (s, 1H),
82.75, 73.99,







3.73 (dd, J = 8.9, 6.4 Hz,
73.75, 52.19,







1H), 3.64-3.44 (m,
30.81, 29.92,







2H), 2.49 (s, 1H),
28.22, 28.21,







2.31-2.02 (m, 1H),
22.42, 18.19,







1.81-1.50 (m, 3H)
17.80, 13.95.







1.43 (p, J = 7.4 Hz,








5H), 1.30-1.08 (m,








3H), 1.01-0.88 (m,








1H), 0.84 (t, J = 7.4 Hz,








1H),








0.82-0.77 (m, 2H), 0.67 (t, J = 7.4 Hz,








1H)



F190
White Solid
—
—
Ammonium Salt:
—
—






ESIMS








m/z 311.3








([M + H]+)




F191
White Solid
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
7.32-7.23 (m, 2H),
(CDCl3) δ






[M + H]+
6.98 (t, J = 7.3 Hz,
169.76,






calcd for
1H), 6.89 (d, J = 8.1 Hz,
156.89,






C19H25F3NO4,
2H), 6.32 (dt, J = 15.8,
136.21 (q, J = 6.3 Hz),






388.1730;
2.0 Hz, 1H),
129.66,






found,
5.89-5.71 (m, 1H),
122.88 (q, J = 269.0 Hz),






388.1738
4.94 (dd, J = 9.4, 6.4 Hz,
121.76,







1H), 4.42 (d, J = 15.9 Hz,
118.52 (q, J = 34.0 Hz),







2H),
116.41, 83.47,







4.34-4.20 (m, 1H), 4.01 (t,
82.35, 73.29,







J = 8.7 Hz, 1H),
70.99, 51.73,







3.78-3.59 (m, 1H),
30.69, 28.06,







3.31-1.85 (m, 5H),
17.78, 17.64







1.84-1.50 (m, 3H),








1.46 (d, J = 6.3 Hz, 3H),








0.99 (dd, J = 16.4,








6.4 Hz, 1H)



F192
White Solid
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
7.27 (dd, J = 8.5, 7.4 Hz,
(CDCl3) δ






[M + H]+
2H), 6.97 (t, J = 7.4 Hz,
169.81,






calcd for
1H),
157.11,






C19H27F3NO4,
6.92-6.84 (m, 2H),
129.61,






390.1187;
4.88 (dt, J = 9.5, 6.3 Hz,
127.07 (q, J = 276.1 Hz),






found,
1H), 4.42-4.30 (m,
121.53,






390.1889
1H), 3.99 (dd, J = 10.4,
116.17, 83.33,







7.6 Hz, 1H),
82.14, 73.59,







3.86-3.65 (m, 2H),
71.85, 51.73,







3.60 (dd, J = 9.5, 7.3 Hz,
30.73,







1H), 2.47 (dt, J = 13.6,
30.58 (q, J = 28.7 Hz),







6.8 Hz, 1H),
28.12,







2.19 (dt, J = 15.7, 7.0 Hz,
22.84 (q, J = 2.7 Hz),







1H), 2.01 (dddd,
17.72, 17.62







J = 29.9, 14.5, 7.2,








3.2 Hz, 2H),








1.80-1.60 (m, 4H), 1.56 (q,








J = 11.5 Hz, 1H),








1.45 (d, J = 6.4 Hz,








3H), 0.98 (dd, J = 16.1,








7.1 Hz, 1H)



F193
White Solid
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.66 (s, 3H),
(CDCl3) δ






[M + H]+
7.28-7.16 (m, 4H),
170.06,






calcd for
7.16-7.10 (m, 1H),
157.40,






C24H32NO4,
7.09-7.01 (m, 2H), 6.93 (t,
141.85,






398.2326;
J = 7.3 Hz, 1H),
129.57,






found,
6.88 (d, J = 8.0 Hz, 2H),
128.33,






398.2324
4.86 (s, 1H), 4.36 (s,
128.27,







1H), 4.10 (s, 1H),
125.73,







3.86-3.72 (m, 1H),
121.32,







3.67-3.53 (m, 2H),
116.39, 83.31,







2.54 (q, J = 13.1,
82.52, 73.72,







10.3 Hz, 3H), 2.18 (s,
73.12, 67.10,







1H), 1.77 (dq, J = 15.2,
32.30, 31.85,







8.5, 7.5 Hz,
30.84, 28.21,







5H), 1.44 (d, J = 4.9 Hz,
17.92, 17.79







3H), 0.98 (d, J = 9.1 Hz,








1H)



F194
White Solid
—
2923,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





1750,
(m/z)
8.69 (s, 3H),
(CDCl3) δ





1507,
[M + H]+
7.00 (dd, J = 12.5, 8.0 Hz,
170.01,





1223
calcd for
4H), 6.92 (d, J = 8.2 Hz,
157.38,






C23H30NO4,
2H), 6.72 (d, J = 8.1 Hz,
155.35,






384.2169;
2H), 5.04 (br
130.96,






found,
s, 1H), 4.51 (t, J = 8.0 Hz,
130.94,






384.2172
1H), 4.41 (d, J = 8.4 Hz,
129.91,







1H),
129.89,







4.22-3.99 (m, 1H),
116.84,







3.82-3.74 (m, 1H), 3.70 (s,
116.38, 82.46,







3H), 2.55 (s, 1H),
82.43, 73.59,







2.24 (d, J = 8.9 Hz,
72.26, 71.12,







6H), 1.41-1.32 (m,
61.69, 59.45,







3H), 1.07 (d, J = 14.0 Hz,
52.31, 42.91,







1H)
30.95, 28.17,








20.49, 18.12,








17.87


F195
White Solid
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.70 (s, 3H),
(CDCl3) δ






[M + H]+
7.31-7.18 (m, 2H), 7.05 (d,
170.13,






calcd for
J = 7.8 Hz, 2H),
159.55,






C18H28NO4,
6.95 (t, J = 7.3 Hz, 1H),
129.36,






322.2013;
4.97 (dt, J = 12.8, 6.4 Hz,
121.43,






found,
1H), 4.36 (dd, J = 9.4,
116.41, 82.76,






322.2019
7.3 Hz, 1H),
82.67, 73.60,







4.16-4.04 (m, 1H),
71.39, 52.31,







3.60-3.48 (m, 1H),
31.03, 28.13,







3.43 (dt, J = 8.9, 6.6 Hz,
23.12, 18.01,







1H), 3.21 (dt, J = 9.0,
17.91, 10.53







6.5 Hz, 1H),








2.65-2.47 (m, 1H),








2.21 (dd, J = 15.1, 5.7 Hz,








1H), 1.77 (dd, J = 41.7,








9.2 Hz, 3H),








1.41 (h, J = 7.4 Hz,








2H), 1.34 (d, J = 6.4 Hz,








3H), 0.99 (dd, J = 15.3,








5.1 Hz, 1H),








0.75 (t, J = 7.4 Hz,








3H)



F196
Off-White
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Solid


(m/z)
8.71 (s, 3H), 7.24 (td,
(CDCl3) δ






[M + H]+
J = 8.9, 7.3 Hz, 4H),
170.13,






calcd for
7.17-7.11 (m, 1H),
159.51,






C24H32NO4,
7.08-6.98 (m, 4H),
141.94,






398.2326;
6.95 (t, J = 7.3 Hz,
129.45,






found,
1H), 4.98 (dq, J = 12.5,
128.39,






398.2332
6.0 Hz, 1H),
128.23,







4.46-4.33 (m, 1H),
125.67,







4.12 (s, 1H),
121.50,







3.51 (ddd, J = 12.1, 9.6,
116.28, 82.91,







5.9 Hz, 2H), 3.22 (dt,
82.28, 73.64,







J = 9.1, 6.1 Hz, 1H),
68.59, 52.30,







3.03-2.52 (m, 2H),
32.14, 31.51,







2.52-2.41 (m, 2H),
31.05, 27.99,







2.33-2.11 (m, 1H),
18.01, 17.90







1.70 (dq, J = 12.8,








6.2 Hz, 4H), 1.34 (d,








J = 6.3 Hz, 3H),








0.98 (d, J = 16.2 Hz, 1H)



F197
White Solid
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.72 (s, 3H),
(CDCl3) δ






[M + H]+
7.31-7.21 (m, 2H),
170.10,






calcd for
6.97 (dd, J = 15.9, 7.9 Hz,
159.18,






C19H27F3NO4,
3H), 5.03-4.93 (m,
129.49,






390.1187;
1H), 4.39 (t, J = 8.2 Hz,
127.14 qd, J = 276.1 Hz),






found,
1H), 4.14 (s, 1H),
121.66,






390.1892
3.54 (s, 2H),
115.96, 83.18,







3.35-3.14 (m, 1H), 2.59 (s,
81.84, 73.48,







1H), 2.30-2.04 (m,
67.63, 52.32,







1H), 1.97-1.76 (m,
30.99,







3H), 1.71 (s, 2H),
30.38 (q, J = 28.9 Hz),







1.61 (p, J = 7.6, 7.0 Hz,
28.09,







2H), 1.36 (d, J = 6.0 Hz,
22.55 (q, J = 2.8 Hz),







3H),
17.94, 17.88







1.11-0.94 (m, 1H)



F198
White Solid
—
—
ESIMS
—
—






m/z 314.3








([M + H]+)




F199
White Solid
—
—
ESIMS
—
—






m/z 382.3








([M + H]+)




F200
White Solid
—
—
HRMS-ESI (m/z)
1H NMR (CDCl3) δ
13C NMR






[M + H]+ calcd for
8.67 (s, 3H),
(CDCl3) δ






C18H34NO4,
4.69 (dq, J = 12.5, 6.0 Hz,
170.12, 84.08,






328.2482,
1H), 4.29 (s, 1H),
83.15, 80.97,






328.2492
4.02 (s, 1H),
75.84, 74.26,







3.41 (dd, J = 9.4, 7.0 Hz,
52.26, 32.92,







1H), 3.32-3.24 (m,
32.27, 31.05,







1H), 3.24-3.17 (m,
28.88, 27.51,







1H), 3.12 (dd, J = 8.6,
23.24, 23.16,







6.0 Hz, 1H),
19.62, 19.46,







2.51 (s, 1H),
18.05, 17.85







2.20-2.06 (m, 1H),








1.89-1.46 (m, 12H), 1.37 (d, J = 6.3 Hz,








3H), 0.90 (dd,








J = 6.7, 4.2 Hz, 6H),








0.82 (d, J = 14.6 Hz,








1H)



F201
White Solid
—
—
ESIMS
—
—






m/z 340.3








([M + H]+)




F202
White Solid
—
—
ESIMS
—
—






m/z 368.3








([M + H]+)




F203
White Solid
—
2959,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2936,
(m/z)
8.69 (br s, 3H),
(CDCl3) δ





2878,
[M + H]+
4.74 (t, J = 7.2 Hz, 1H),
169.99, 83.91,





1751,
calcd for
4.01-3.97 (m, 1H),
83.53, 75.52,





1207
C15H30NO4,
3.75 (dt, J = 8.9, 6.5 Hz,
74.21, 70.90,






288.2169;
1H), 3.51 (ddt, J = 29.8,
52.10, 31.28,






found,
9.0, 6.6 Hz,
27.87, 23.49,






288.2167
2H), 3.35-3.15 (m
23.33, 17.81,







3H) 2.56-2.45 (m,
17.77, 10.76,







1H) 2.11 (s, 1H),
10.67







1.75-1.47 (m, 7H),








1.39 (d, J = 6.2 Hz,








3H), 0.92 (td, J = 7.4,








1.8 Hz, 6H),








0.86-0.71 (m, 1H)



F204
White Solid
—
—
ESIMS
1H NMR (CD3OD) δ
13C NMR






m/z 314
4.72 (dq, J = 9.4, 6.3 Hz,
(CD3OD) δ






([M + H]+)
1H), 4.32 (td, J = 4.8,
171.27, 85.26,







2.6 Hz, 1H),
84.55, 82.36,







3.94 (dd, J = 10.6, 7.0 Hz,
75.48, 71.88,







1H), 3.52 (dt, J = 8.8,
52.90, 33.91,







6.7 Hz, 1H), 3.44 (dd,
33.32, 31.94,







J = 9.4, 6.9 Hz, 1H),
28.66, 24.48,







3.36-3.24 (m, 2H),
24.27, 24.25,







2.36-2.13 (m, 2H),
18.90, 18.48,







1.88-1.76 (m, 1H),
11.24







1.76-1.42 (m, 12H),








1.39 (d, J = 6.4 Hz,








3H), 0.94 (t, J = 7.4 Hz,








3H), 0.84 (dt, J = 15.9,








4.3 Hz, 1H)



F205
White Solid
—
—
ESIMS
1H NMR (CD3OD) δ
—






m/z 368
4.91-4.84 (m, 1H),







([M + H]+)
4.78 (ddd, J = 7.8,








6.0, 2.1 Hz, 1H),








4.21-4.11 (m, 1H),








3.97 (dd, J = 10.8, 7.1 Hz,








1H), 3.62 (dd, J = 9.4,








7.4 Hz, 1H),








2.78 (ddd, J = 15.6, 8.5,








7.2 Hz, 1H),








2.27 (dtd, J = 13.9, 7.0,








1.9 Hz, 1H),








2.17-2.04 (m, 1H),








2.00-1.90 (m, 1H),








1.90-1.79 (m, 2H),








1.79-1.45 (m, 16H),








1.44 (d, J = 6.5 Hz, 3H),








1.16-1.03 (m, 1H)



F206
White Solid
—
3398,
ESIMS
1H NMR (CD3OD) δ
—





2924,
m/z 366
7.04-6.89 (m, 4H),






1749,
([M + H]+)
4.32-4.26 (m, 2H),






1503

3.99 (dd, J = 10.7,








7.2 Hz, 1H),








3.77-3.63 (m, 2H),








2.34-2.10 (m, 2H),








1.88-1.39 (m, 11H),








1.47 (d, J = 6.4 Hz, 3H),








0.98 (dd, J = 16.4,








7.6 Hz, 1H)



F207
White Solid
—
—
ESIMS
—
—






m/z 390.4








([M + H]+)




F208
White Solid
—
—
ESIMS
—
—






m/z 342.3








([M + H]+)




F209
White Solid
—
—
ESIMS
—
—






m/z 378.3








([M + H]+)




F210
White Solid
—
—
ESIMS
1H NMR (CDCl3) δ
13C NMR






m/z 493.1
12.09 (s, 1H),
(CDCl3) δ






([M + H]+),
8.48 (d, J = 8.1 Hz, 1H),
172.09,






m/z 515.2
7.99 (d, J = 5.2 Hz,
168.65,






([M + Na]+)
1H), 6.86 (d, J = 5.2 Hz,
155.34,







1H), 4.77 (dq, J = 9.7,
148.72,







6.4 Hz, 1H),
140.51,







4.58 (dt, J = 10.8, 7.7 Hz,
130.43,







1H), 3.94 (s, 3H),
109.45, 84.71,







3.69-3.58 (m, 1H),
80.34, 79.29,







3.54 (dd, J = 9.6, 7.0 Hz,
75.87, 73.45,







1H), 3.34 (t, J = 5.6 Hz,
56.07, 51.32,







1H), 3.27 (dd,
33.52, 33.35,







J = 8.6, 6.7 Hz, 1H),
32.69, 28.93,







3.12 (dd, J = 8.6, 6.2 Hz,
27.45, 25.76,







1H), 2.36 (dd, J = 13.4,
24.55, 24.45,







6.5 Hz, 1H),
19.63, 19.54,







2.23-2.07 (m, 1H),
18.27, 18.25







1.98 (dd, J = 13.6,








8.8 Hz, 2H),








1.89-1.59 (m, 5H), 1.55 (d,








J = 9.7 Hz, 1H),








1.45-1.31 (m, 4H),








1.31-1.10 (m, 5H),








0.92 (d, J = 6.7 Hz, 7H)



F211
White Solid
—
—
ESIMS
1H NMR (CDCl3) δ
13C NMR






m/z 493.1
12.09 (s, 1H),
(CDCl3) δ






([M + H]+),
8.46 (d, J = 8.1 Hz, 1H),
172.09,






m/z 515.2
7.99 (d, J = 5.2 Hz,
168.65,






([M + Na])
1H), 6.86 (d, J = 5.2 Hz,
155.36,







1H), 4.80 (dq, J = 9.8,
148.74,







6.5 Hz, 1H),
140.50,







4.58 (dt, J = 10.8, 7.6 Hz,
130.43,







1H), 3.94 (s, 3H),
109.46, 83.81,







3.69 (dd, J = 8.5, 6.0 Hz,
80.99, 76.00,







1H),
73.61, 56.07,







3.60-3.43 (m, 1H), 3.34 (ddd, J = 8.4,
51.32, 33.78,







7.2, 3.9 Hz,
33.43, 32.32,







3H), 2.37 (dt, J = 14.0,
29.18, 29.13,







7.0 Hz, 1H),
25.78, 24.43,







2.04 (ddd, J = 21.2,
24.24, 19.63,







9.4, 5.0 Hz, 1H),
19.45, 18.50,







1.91 (t, J = 8.8 Hz, 1H),
17.93







1.83 (dt, J = 13.0, 6.6 Hz,








2H),








1.78-1.63 (m, 4H), 1.60 (s, 1H),








1.41 (d, J = 6.4 Hz,








3H), 1.38-1.12 (m,








7H), 0.91 (dd, J = 9.5,








6.7 Hz, 6H)



F212
White Solid
109-111
3368,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2956,
(m/z)
12.09 (s, 1H),
(CDCl3) δ





2874,
[M + Na]+
8.47 (d, J = 8.1 Hz, 1H),
172.05,





1743,
calcd for
7.99 (d, J = 5.2 Hz,
168.64,





1650,
C23H36N2NaO7,
1H), 6.87 (d, J = 5.1 Hz,
155.34,





1528,
475.2415;
1H),
148.72,





1100
found,
4.89-4.67 (m, 1H), 4.58 (dt, J = 10.8,
140.51,






475.2419
7.6 Hz, 1H),
130.40,







3.94 (s, 3H),
109.45, 84.17,







3.83-3.69 (m, 1H),
83.73, 75.95,







3.57 (dt, J = 8.8, 6.7 Hz,
75.45, 73.30,







1H), 3.41-3.32 (m,
56.07, 51.30,







2H), 3.29 (dd, J = 8.7,
33.35, 28.87,







6.5 Hz, 1H),
27.69, 23.51,







3.13 (dd, J = 8.7, 6.3 Hz,
19.53, 19.48,







1H), 2.43-2.29 (m,
18.22, 17.91,







1H), 2.23-2.04 (m,
10.69







1H), 1.82 (hept, J = 6.6 Hz,








1H),








1.73-1.61 (m, 2H),








1.62-1.52 (m, 3H), 1.41 (d,








J = 6.4 Hz, 3H),








1.40-1.31 (m, 1H),








0.97-0.84 (m, 9H)



F213
White Solid
63-66
3367,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2954,
(m/z)
12.06 (s, 1H),
(CDCl3) δ





2872,
[M + Na]+
8.44 (d, J = 8.0 Hz, 1H),
173.91,





1734,
calcd for
7.99 (d, J = 5.2 Hz,
172.11,





1528,
C24H34N2NaO8,
1H), 6.87 (d, J = 5.3 Hz,
168.65,





1166
501.2207;
1H), 5.16 (dd, J = 9.7,
155.37,






found,
7.8 Hz, 1H),
148.76,






501.2209
4.97 (dq, J = 9.8, 6.4 Hz,
140.50,







1H), 4.62 (dt, J = 10.7,
130.36,







7.6 Hz, 1H),
109.48, 81.12,







3.94 (s, 3H),
76.34, 75.56,







3.39 (ddd, J = 7.6, 5.3, 1.9 Hz,
71.77, 56.08,







1H), 3.31 (dd, J = 8.8,
51.29, 33.33,







6.1 Hz, 1H),
28.64, 28.00,







2.99 (dd, J = 8.8, 6.8 Hz,
19.31, 19.26,







1H), 2.40 (ddd, J = 13.8,
17.98, 17.22,







7.6, 6.2 Hz,
12.87, 8.48,







1H), 2.17 (dddd, J = 15.7,
8.40







10.1, 7.9, 5.3 Hz,








1H),








1.86-1.60 (m, 4H),








1.47-1.33 (m, 1H), 1.30 (d, J = 6.4 Hz,








3H),








1.07-0.96 (m, 3H),








0.92-0.81 (m, 8H)



F214
Colorless
—
2949,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Oil

2871,
(m/z)
8.53 (s, 1H), 8.33 (d,
(CDCl3) δ





1772,
[M + Na]+
J = 5.5 Hz, 1H),
172.55,





1743,
calcd for
7.31-7.27 (m, 2H),
162.38,





1679,
C31H42N2NaO8,
7.22-7.15 (m, 3H),
159.43,





1507,
593.2833;
7.00 (d, J = 5.5Hz, 1H),
146.69,





1197
found,
4.85-4.73 (m, 1H),
142.05,






593.2832
4.59 (dt, J = 10.8, 7.7 Hz,
141.43,







1H), 3.91 (s, 3H),
137.48,







3.84 (dt, J = 9.1, 6.4 Hz,
128.35,







1H), 3.63 (dt, J = 9.1,
128.32,







6.5 Hz, 1H),
125.76,







3.41-3.31 (m, 2H),
109.77, 84.25,







3.26 (dd, J = 8.7, 6.6 Hz,
83.89, 75.83,







1H), 3.09 (dd, J = 8.8,
73.00, 72.93,







6.3 Hz, 1H),
56.28, 51.35,







2.68 (td, J = 7.6, 4.3 Hz,
33.63, 32.52,







2H), 2.40 (s, 3H),
32.01, 28.84,







2.39-2.27 (m, 1H),
27.71, 20.75,







2.19-2.04 (m, 1H),
19.54, 19.49,







1.90 (dtd, J = 8.6,
18.24, 17.98







6.7, 1.8 Hz, 2H),








1.78 (dt, J = 13.2, 6.6 Hz,








1H), 1.68-1.59 (m,








2H), 1.39 (d, J = 6.3 Hz,








3H),








1.36-1.24 (m, 2H), 0.88 (dd, J = 6.7,








2.5 Hz, 6H)



F215
Colorless
—
2948,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Semi-Solid

1769,
(m/z)
8.50 (s, 1H), 8.33 (d,
(CDCl3) δ





1743,
[M + H]+
J = 5.4 Hz, 1H),
172.55,





1679,
calcd for
7.32-7.24 (m, 2H),
169.44,





1507,
C33H47N2O9,
7.24-7.10 (m, 3H),
162.33,





1106
615.3276;
6.99 (d, J = 5.5 Hz, 1H),
159.44,






found,
4.87-4.71 (m, 1H),
146.74,






615.3298
4.58 (dt, J = 10.8, 7.8 Hz,
142.05,







1H), 3.90 (s, 3H),
141.47,







3.87-3.74 (m, 3H),
137.33,







3.74-3.54 (m, 1H),
128.35,







3.41 (s, 3H),
128.32,







3.37-3.27 (m, 2H),
125.76,







3.27-3.20 (m, 1H),
83.90, 75.82,







109.76, 84.24,
72.99, 72.91,







3.09 (dd, J = 8.7, 6.3 Hz,
67.58, 58.80,







1H), 2.98 (t, J = 6.6 Hz,
56.31, 51.33,







2H), 2.68 (td, J = 7.8,
34.62, 33.62,







4.3 Hz, 2H),
32.52, 32.01,







2.40-2.27 (m, 1H),
29.71, 28.85,







2.18-2.04 (m, 1H),
27.70, 19.54,







1.95-1.84 (m, 2H),
19.49, 18.24,







1.78 (dt, J = 13.2, 6.6 Hz,
17.99







1H), 1.69-1.57 (m,








2H), 1.39 (d, J = 6.3 Hz,








3H),








1.36-1.18 (m, 2H), 0.88 (dd, J = 6.6,








2.6 Hz, 6H)



F216
White Solid
—
2954,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2874,
(m/z)
8.52 (d, J = 10.1 Hz,
(CDCl3) δ





1772,
[M + H]+
1H), 8.33 (d, J = 5.5 Hz,
172.51,





1744,
calcd for
1H), 7.00 (d, J = 5.4 Hz,
168.92,





1679,
C26H38F3N2O8,
1H),
162.40,





1508,
563.2575;
4.84-4.71 (m, 1H),
159.44,





1198
found,
4.59 (dt, J = 10.7, 7.7 Hz,
146.69,






563.2587
1H), 3.91 (s, 3H),
141.39,







3.85 (dt, J = 9.3, 6.1 Hz,
137.49,







1H), 3.67 (dt, J = 9.4,
109.79, 84.07,







6.1 Hz, 1H),
83.99, 75.64,







3.39-3.29 (m, 2H),
72.68, 71.67,







3.27 (dd, J = 8.7, 6.7 Hz,
56.29, 51.33,







1H), 3.08 (dd, J = 8.7,
33.59, 31.05,







6.2 Hz, 1H),
30.76, 28.87,







2.40 (s, 3H), 2.34 (dd, J = 13.8,
27.48,







6.7 Hz, 1H),
23.1-23.00 (m),







2.25-2.05 (m, 3H),
20.76, 19.54,







1.87-1.75 (m, 3H),
19.47, 18.18,







1.71-1.59 (m, 2H),
17.93;







1.37 (d, J = 6.4 Hz,
19F NMR







3H), 1.34-1.22 (m,
(CDCl3) δ







1H), 0.91 (dd, J = 6.7,
−66.43 (t, J = 10.9 Hz)







1.3 Hz, 6H),








0.91-0.83 (m, 1H)



F217
Yellow Oil
—
3380,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2952,
(m/z)
8.32 (d, J = 8.1 Hz,
(CDCl3) δ





1745,
[M]+
1H), 8.27 (d, J = 5.3 Hz,
172.74,





1677,
calcd for
1H), 6.95 (d, J = 5.4 Hz,
170.23,





1504,
C29H42N2O9,
1H), 5.74 (s,
162.94,





1202
562.2890;
2H), 4.73 (dq, J = 8.9,
160.25,






found,
6.5 Hz, 1H),
145.71,






562.2908
4.60 (dt, J = 10.8, 7.6 Hz,
143.94,







1H), 4.33 (qd, J = 5.1,
142.41,







4.7, 3.4 Hz, 1H),
109.59, 89.52,







4.02 (qd, J = 5.4, 3.8 Hz,
83.28, 81.81,







1H), 3.91 (s, 3H),
81.07, 78.94,







3.46-3.36 (m, 2H),
73.44, 56.17,







2.37 (dtd, J = 13.5,
51.65, 33.52,







6.7, 1.6 Hz, 1H),
33.45, 32.77,







2.15-2.06 (m, 1H),
32.43, 31.73,







2.07 (s, 3H),
28.38, 23.71,







1.84-1.43 (m, 18H), 1.38 (d, J = 6.4 Hz,
23.40, 23.33,







3H), 1.32 (dt,
23.30, 20.85,







J = 10.8, 2.3 Hz, 1H),
18.59, 18.08







0.90 (ddt, J = 15.8,








7.4, 1.8 Hz, 1H)



F218
White Foam
—
3377,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR





2955,
(m/z)
8.35 (d, J = 8.0 Hz,
(CDCl3) δ





1740,
[M + H]+
1H), 8.27 (d, J = 5.3 Hz,
176.29,





1679
calcd for
1H), 6.94 (d, J = 5.4 Hz,
175.57,






C31H47N2O10,
1H),
172.73,






607.3225;
5.82-5.70 (m, 2H),
162.93,






found,
5.16 (dd, J = 9.8, 7.8 Hz,
160.26,






607.3241
1H), 4.95 (dq, J = 9.8,
145.55,







6.5 Hz, 1H),
141.99,







4.63 (dt, J = 10.9, 7.6 Hz,
109.54, 89.93,







1H), 3.89 (s, 3H),
81.19, 76.12,







3.37 (ddd, J = 7.5,
75.36, 71.47,







5.3, 1.9 Hz, 1H),
56.13, 51.63,







3.27 (dd, J = 8.6, 6.3 Hz,
43.98, 33.86,







1H), 3.01-2.93 (m,
33.38, 30.13,







1H), 2.73 (p, J = 7.9 Hz,
29.76, 28.69,







1H), 2.55 (p, J = 7.0 Hz,
27.84, 25.82,







1H), 2.40 (dt,
25.72, 19.37,







J = 13.7, 7.0 Hz, 1H),
19.34, 18.68,







2.22-2.10 (m, 1H),
18.04, 17.26







1.95-1.41 (m, 11H),








1.36 (q, J = 11.7 Hz,








1H), 1.26 (d, J = 7.9,








3H), 1.14 (d, J = 6.9 Hz,








6H),








1.07-0.96 (m, 1H), 0.85 (d, J = 6.7 Hz,








6H)



F219
Colorless
—
3367,
HRMS-ESI
1HNMR (CDCl3) δ
13CNMR



Oil

2949,
(m/z)
12.09 (s, 1H),
(CDCl3) δ





2870,
[M + H]+
8.48 (d, J = 8.2 Hz, 1H),
172.03,





1742,
calcd for
7.98 (d, J = 5.1 Hz,
168.66,





1649,
C29H41N2O7,
1H), 7.34-7.24 (m,
155.34,





1526,
529.2908;
2H), 7.24-7.15 (m,
148.72,





1497
found,
3H), 6.86 (d, J = 5.2 Hz,
142.00,






529.2912
1H), 4.82 (dtd, J = 12.7,
140.52,







6.3, 2.0 Hz,
130.40,







1H), 4.59 (dt, J = 10.8,
128.40,







7.6 Hz, 1H),
128.34,







3.94 (s, 3H),
125.80,







3.63 (dd, J = 8.7, 6.2 Hz,
109.47, 84.30,







1H), 3.56 (dt, J = 9.1,
83.75, 80.69,







6.4 Hz, 1H),
73.35, 68.34,







3.43-3.33 (m, 4H),
56.08, 51.31,







2.70 (dd, J = 8.8, 6.7 Hz,
49.34, 33.35,







2H), 2.37 (dtd, J = 13.7,
32.53, 31.81,







6.8, 1.6 Hz,
29.11, 27.88,







1H), 2.19-2.05 (m,
19.54, 19.49,







1H), 1.97-1.78 (m,
19.43, 18.26,







3H), 1.78-1.59 (m,
17.99







2H), 1.42 (d, J = 6.3 Hz,








3H),








1.40-1.31 (m, 1H), 0.91 (d, J = 6.6 Hz,








3H), 0.89 (d,








J = 6.7 Hz, 3H),








0.90-0.87 (m, 1H)



F220
White Solid

3366,
HRMS-ESI
1H NMR (CDCl3) δ
13CNMR





2954,
(m/z)
12.09 (s, 1H),
(CDCl3) δ





2872,
[M + H]+
8.48 (d, J = 8.2 Hz, 1H),
172.03,





1742,
calcd for
7.99 (d, J = 5.2 Hz,
168.65,





1649,
C24H37N2O7,
1H), 6.87 (d, J = 5.2 Hz,
155.34,





1526
465.2605;
1H), 4.98 (s, 1H),
148.71,






found,
4.87 (t, J = 1.8 Hz,
142.48,






465.2595
1H), 4.86-4.77 (m,
140.51,







1H), 4.59 (dt, J = 10.7,
130.38,







7.6 Hz, 1H),
112.11,







3.96 (d, J = 11.7 Hz,
109.46, 83.78,







1H), 3.94 (s, 3H),
83.60, 80.67,







3.85 (d, J = 12.0 Hz,
73.37, 73.25,







1H), 3.64 (dd, J = 8.6,
56.07, 51.31,







6.1 Hz, 1H),
33.30, 29.11,







3.48-3.33 (m, 3H),
27.97, 19.71,







2.37 (dtd, J = 13.8, 7.1,
19.53, 19.38,







6.7, 1.8 Hz, 1H),
18.28, 17.96







2.23-2.05 (m, 1H),








1.83 (dq, J = 13.8, 6.9 Hz,








1H), 1.76 (s, 3H),








1.76-1.63 (m, 2H),








1.42 (d, J = 6.4 Hz,








3H), 1.39-1.32 (m,








1H), 0.99-0.93 (m,








1H), 0.92 (d, J = 6.7 Hz,








3H), 0.90 (d, J = 6.7 Hz,








3H);



F221
White Solid
129-130
3384,
HRMS-ESI
1H NMR (CDCl3) δ
13CNMR





2954,
(m/z)
12.04 (s, 1H),
(CDCl3) δ





2871,
[M + H]+
8.49 (d, J = 8.2 Hz, 1H),
175.71,





1735,
calcd for
7.99 (d, J = 5.2 Hz,
171.76,





1655,
C26H39N2O8,
1H), 6.87 (d, J = 5.2 Hz,
168.68,





1526,
507.2712;
1H),
155.33,





1447
found,
4.99-4.84 (m, 2H),
148.69,






507.2701
4.61 (ddd, J = 10.8, 8.2,
140.57,







7.2 Hz, 1H), 3.94 (s,
130.32,







3H), 3.50 (dd, J = 9.5,
109.50, 82.23,







7.6 Hz, 1H),
80.27, 77.63,







3.43-3.32 (m, 2H),
73.12, 56.08,







2.80-2.66 (m, 1H),
51.21, 44.09,







2.36 (dtd, J = 13.5, 7.2, 1.4 Hz,
33.16, 30.24,







1H), 2.14 (dddd,
29.76, 29.13,







J = 15.9, 10.0, 7.8,
29.01, 25.80,







5.5 Hz, 1H),
25.79, 19.36,







1.98-1.54 (m, 11H),
19.29, 18.32,







1.44 (d, J = 6.4 Hz, 3H),
17.90







1.42-1.33 (m, 1H),








1.10 (ddt, J = 16.3,








7.4, 2.2 Hz, 1H),








0.88 (d, J = 7.0 Hz, 3H),








0.86 (d, J = 6.9 Hz,








3H)



F222
Colorless
—
3380,
HRMS-ESI
1HNMR (CDCl3) δ
13CNMR



Oil

2951,
(m/z)
8.32 (d, J = 8.0 Hz,
(CDCl3) δ





2871,
[M + H]+
1H), 8.27 (d, J = 5.4 Hz,
172.63,





1748,
calcd for
1H),
170.27,





1678,
C32H45N2O9,
7.33-7.25 (m, 2H),
162.98,





1502
601.3127;
7.23-7.12 (m, 3H), 6.94 (d,
160.27,






found,
J = 5.4 Hz, 1H),
145.74,






601.3120
5.74 (s, 2H), 4.79 (ddd, J = 10.7,
143.98,







6.7, 3.7 Hz,
142.41,







1H), 4.61 (dt, J = 10.8,
142.01,







7.5 Hz, 1H),
128.40,







3.90 (s, 3H),
128.34,







3.63 (dd, J = 8.7, 6.1 Hz,
128.31,







1H), 3.56 (dt, J = 9.1,
125.77,







6.4 Hz, 1H),
109.61, 89.54,







3.43-3.30 (m, 4H),
84.37, 83.79,







2.70 (dd, J = 8.8, 6.7 Hz,
80.67, 73.07,







2H), 2.46-2.30 (m,
68.29, 56.19,







1H), 2.10 (dd, J = 5.3,
51.63, 33.42,







3.1 Hz, 1H),
32.53, 31.80,







2.07 (s, 3H),
29.10, 27.94,







1.94-1.78 (m, 4H),
20.88, 19.55,







1.78-1.57 (m, 1H), 1.40 (d, J = 6.3 Hz,
19.43, 18.32,







3H),
17.98







1.38-1.26 (m, 1H),








0.96-0.93 (m, 1H), 0.91 (d,








J = 7.2 Hz, 3H),








0.89 (d, J = 6.9 Hz, 3H)



F223
White Solid
35-39
3379,
HRMS-ESI
1HNMR (CDCl3) δ
13CNMR





2954,
(m/z)
8.34 (d, J = 8.1 Hz,
(CDCl3) δ





2872,
[M + H]+
1H), 8.27 (d, J = 5.4 Hz,
175.70,





1732,
calcd for
1H), 6.96 (d, J = 5.4 Hz,
172.35,





1677,
C29H43N2O10,
1H),
170.23,





1502
579.2910;
5.74 (s, 2H),
162.98,






found,
4.97-4.84 (m, 2H), 4.63 (dt, J = 10.7,
160.23,






579.2912
7.5 Hz, 1H),
145.75,







3.91 (s, 3H),
143.90,







3.49 (dd, J = 9.6, 7.5 Hz,
142.28,







1H), 3.44-3.30 (m,
109.66, 89.44,







2H), 2.81-2.67 (m,
82.25, 80.23,







1H), 2.43-2.29 (m,
77.72, 72.81,







1H), 2.20-2.09 (m,
56.19, 51.52,







1H), 2.08 (s, 3H),
44.07, 33.19,







2.00-1.54 (m, 11H),
30.21, 29.73,







1.42 (d, J = 6.4 Hz,
29.17, 28.98,







3H), 1.40-1.29 (m,
25.77, 25.76,







1H), 1.09 (ddt, J = 16.5,
20.85, 19.34,







7.8, 2.2 Hz,
19.27, 18.36,







1H), 0.88 (d, J = 6.3 Hz,
17.87







3H), 0.86 (d, J = 6.6 Hz,








3H)



F224
Colorless
—
3368,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Oil

2934,
(m/z)
12.09 (s, 1H),
(CDCl3) δ





1743,
[M + H]+
8.48 (d, J = 8.1 Hz, 1H),
172.09,





1529
calcd for
7.98 (d, J = 5.2 Hz,
168.66,






C30H41N2O7,
1H), 7.33-7.23 (m,
155.33,






541.2908;
2H), 7.23-7.15 (m,
148.70,






found,
3H), 6.86 (d, J = 5.2 Hz,
141.98,






541.2919
1H), 4.76 (dq, J = 9.6,
140.53,







6.4 Hz, 1H),
130.38,







4.59 (dt, J = 10.8, 7.6 Hz,
128.38,







1H), 4.37-4.26 (m,
128.34,







1H), 3.93 (s, 3H),
125.81,







3.55 (dt, J = 9.1, 6.6 Hz,
109.48, 84.32,







1H), 3.48 (dd, J = 9.6,
83.39, 81.26,







7.1 Hz, 1H),
73.54, 68.41,







3.40-3.28 (m, 2H),
56.07, 51.33,







2.80-2.61 (m, 2H),
33.31, 32.94,







2.41-2.32 (m, 1H),
32.53, 32.41,







2.16-2.05 (m, 1H),
31.77, 27.82,







1.98-1.86 (m, 2H),
23.30, 23.24,







1.86-1.46 (m, 10H),
18.29, 18.11







1.40 (d, J = 6.5 Hz, 3H),








1.38-1.29 (m, 1H),








0.96-0.86 (m, 1H)



F225
Colorless
—
3378,
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Oil

2939,
(m/z)
8.33 (d, J = 8.0 Hz,
(CDCl3) δ





2868,
[M + H]+
1H), 8.27 (d, J = 5.3 Hz,
172.69,





1748,
calcd for
1H),
170.26,





1678
C33H45N2O9,
7.33-7.23 (m, 2H),
162.97,






613.3120;
7.23-7.13 (m, 3H), 6.94 (d, J = 5.4 Hz,
160.26,






found,
1H), 5.74 (s,
145.73,






613.3133
2H), 4.74 (dq, J = 9.5,
143.96,







6.4 Hz, 1H),
142.41,







4.61 (dt, J = 10.7, 7.5 Hz,
142.01,







1H), 4.36-4.26 (m,
128.38,







1H), 3.90 (s, 3H),
128.32,







3.55 (dt, J = 9.0, 6.6 Hz,
125.78,







1H), 3.48 (dd, J = 9.6,
109.62, 89.52,







7.0 Hz, 1H),
84.39, 83.36,







3.41-3.27 (m, 2H),
81.32, 73.25,







2.80-2.61 (m, 2H),
68.37, 56.19,







2.45-2.31 (m, 1H),
51.66, 33.40,







2.19-2.08 (m, 1H),
32.94, 32.52,







2.07 (s, 3H),
32.40, 31.76,







1.98-1.85 (m, 2H),
27.91, 23.29,







1.85-1.45 (m, 10H), 1.39 (d, J = 6.4 Hz,
23.23, 20.88,







3H),
18.36, 18.10







1.37-1.28 (m, 1H),








0.96-0.87 (m, 1H)



F226
White Solid
—
—
ESIMS
—
—






m/z 314.3








([M + H]+)




F227
Colorless
—
—
ESIMS
1H NMR (CD3OD) δ
13C NMR



Oil


m/z 382
4.64 (dq, J = 9.4, 6.4 Hz,
(CD3OD) δ






([M + H]+)
1H),
173.78,







4.23-4.18 (m, 1H), 3.85 (dd, J = 10.7,
132.81,







7.3 Hz, 1H),
130.07, 87.79,







3.59-3.50 (m, 1H),
87.15, 84.79,







3.39-3.29 (m, 2H),
78.03, 70.65,







3.27-3.22 (m, 1H),
55.37, 36.36,







2.27-2.05 (m, 4H),
35.85, 34.59,







1.77-1.67 (m, 3H),
34.42, 34.30,







1.66-1.33 (m, 10H),
34.02, 33.73,







1.31 (d, J = 6.4 Hz,
31.08, 26.75,







3H), 0.84-0.70 (m,
26.56, 26.53,







1H)
26.50, 26.47,








21.30, 20.91


F228
White Foam
—
—
ESIMS
1H NMR (CD3OD) δ
13C NMR






m/z 390
7.30-7.22 (m, 2H),
(CD3OD) δ






([M + H]+)
7.21-7.12 (m, 3H),
171.31,







4.73 (dq, J = 9.5, 6.4 Hz,
143.33,







1H),
129.70,







4.37-4.32 (m, 1H), 3.94 (dd, J = 10.7,
129.61,







7.3 Hz, 1H),
127.05, 85.41,







3.58 (dt, J = 9.0, 6.6 Hz,
84.67, 82.45,







1H), 3.47 (dd, J = 9.5,
75.52, 69.77,







7.0 Hz, 1H),
68.43, 53.38,







3.41-3.32 (m, 2H),
34.14, 33.86,







2.79-2.61 (m, 2H),
33.60, 33.36,







2.34-2.10 (m, 2H),
32.37, 29.05,







1.97-1.76 (m, 3H),
24.51, 24.48,







1.76-1.42 (m, 10H),
19.36, 18.90







1.40 (d, J = 6.4 Hz, 3H),








0.85 (dt, J = 16.3, 4.3 Hz,








1H)



F229
Colorless
—
—
ESIMS
1H NMR (CD3OD) δ
13C NMR



Oil


m/z 378.3
6.92-6.80 (m, 4H),
(CD3OD) δ






([M + H]+)
4.86-4.80 (m, 1H),
171.23,







4.31 (tt, J = 5.3, 3.5 Hz,
155.86,







1H), 4.23 (ddd, J = 7.1,
152.78,







5.3, 1.7 Hz,
118.77,







1H), 3.98 (dd, J = 10.8,
115.77, 85.04,







7.5 Hz, 1H),
84.67, 82.11,







3.74 (s, 3H),
75.39, 68.18,







3.75-3.71 (m, 1H),
56.17, 52.86,







2.26 (dt, J = 13.7, 7.1 Hz,
33.86, 33.47,







1H), 2.20-2.12 (m,
31.91, 28.98,







1H), 1.90-1.48 (m,
24.19, 24.13,







10H), 1.46 (d, J = 6.4 Hz,
18.85, 18.43







3H),








1.45-1.35 (m, 1H), 0.93 (ddt, J = 16.2,








7.7, 1.7 Hz,








1H)



F230
White Foam
—
—
ESIMS
1H NMR (CD3OD) δ
13C NMR






m/z 314.4
4.72 (dq, J = 9.4, 6.3 Hz,
(CD3OD)






([M + H]+)
1H), 4.32 (td, J = 4.8,
δ 171.27,







2.6 Hz, 1H),
85.26, 84.55,







3.94 (dd, J = 10.6, 7.0 Hz,
82.36, 75.48,







1H), 3.52 (dt, J = 8.8,
71.88, 52.90,







6.7 Hz, 1H), 3.44 (dd,
33.91, 33.32,







J = 9.4, 6.9 Hz, 1H),
31.94, 28.66,







3.36-3.24 (m, 2H),
24.48, 24.27,







2.36-2.13 (m, 2H),
24.25, 18.90,







1.88-1.76 (m, 1H),
18.48, 11.24







1.76-1.42 (m, 12H),








1.39 (d, J = 6.4 Hz,








3H), 0.94 (t, J = 7.4 Hz,








3H), 0.84 (dt, J = 15.9,








4.3 Hz, 1H)



F231
White Solid
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
7.24 (t, J = 8.0 Hz,
(CDCl3) δ






[M + H]+
2H), 6.94 (t, J = 7.4 Hz,
175.68,






calcd for
1H),
169.87,






C21H30NO5,
6.89-6.79 (m, 2H), 5.35 (dd, J = 9.5,
157.60,






376.2118;
8.1 Hz, 1H),
129.49,






found,
5.06 (dq, J = 12.7, 6.3 Hz,
121.56,






376.2122
1H), 4.48-4.30 (m,
116.40, 79.58,







1H), 4.06 (dd, J = 10.3,
74.57, 72.42,







7.7 Hz, 1H),
51.82, 43.68,







2.56 (ddd, J = 19.5,
30.80, 29.80,







9.7, 3.9 Hz, 5H),
29.70, 28.60,







1.93-1.40 (m, 12H),
25.67, 25.58,







1.33 (d, J = 6.3 Hz, 3H),
17.51, 17.11







1.13 (dd, J = 16.0, 7.1 Hz,








1H)



F232
White Tacky
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Solid


(m/z)
12.03 (s, 1H), 8.45 (d,
(CDCl3) δ






[M + H]+
J = 8.0 Hz, 1H),
175.59,






calcd for
7.98 (d, J = 5.2 Hz, 1H),
172.07,






C28H35N2O8,
7.27-7.22 (m, 2H),
168.71,






527.2388;
6.98-6.92 (m, 1H),
157.75,






found,
6.89-6.84 (m, 3H),
155.38,






527.2400
5.40 (dd, J = 9.7, 7.9 Hz,
148.76,







1H), 5.11 (dq, J = 9.8,
140.54,







6.4 Hz, 1H),
130.29,







4.68 (dt, J = 10.7, 7.6 Hz,
129.50,







1H), 4.41 (ddd, J = 7.5,
121.51,







5.4, 1.8 Hz, 1H),
116.50,







3.94 (s, 3H),
109.53, 79.77,







2.59 (ddd, J = 15.6, 8.3, 7.1 Hz,
74.85, 71.48,







1H), 2.41 (dt, J = 13.7,
56.09, 51.27,







7.1 Hz, 1H),
43.73, 33.16,







2.32-2.18 (m, 1H),
29.84, 29.73,







2.02-1.86 (m, 1H),
28.81, 25.71,







1.80-1.37 (m, 10H),
25.62, 18.02,







1.34 (d, J = 6.4 Hz,
17.30







3H), 1.27-1.14 (m,








1H)



F233
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.31 (d, J = 7.8 Hz,
(CDCl3) δ






[M + H]+
1H), 8.27 (d, J = 5.4 Hz,
175.57,






calcd for
1H), 7.25 (dd, J = 8.7,
172.67,






C31H38N2O10,
7.4 Hz, 2H),
170.30,






599.2599;
6.97-6.91 (m, 2H),
162.99,






found,
6.87 (dd, J = 8.7, 0.9 Hz,
160.30,






599.2600
2H), 5.74 (s, 2H),
157.81,







5.38 (dd, J = 9.8, 7.9 Hz,
145.70,







1H), 5.09 (dq, J = 9.8,
144.10,







6.4 Hz, 1H), 4.69 (dt,
142.24,







J = 10.7, 7.5 Hz, 1H),
129.47,







4.39 (ddd, J = 7.5, 5.4,
121.44,







1.8 Hz, 1H), 3.91 (s,
116.50,







3H), 2.59 (ddd, J = 15.6,
109.66, 89.54,







8.3, 7.1 Hz, 1H),
79.80, 74.95,







2.41 (dt, J = 13.7, 7.1 Hz,
71.18, 56.20,







1H),
51.63, 43.74,







2.30-2.15 (m, 1H), 2.07 (s, 3H),
33.22, 29.84,







2.00-1.86 (m, 1H),
29.73, 28.95,







1.85-1.43 (m, 9H),
25.70, 25.61,







1.42-1.30 (m, 4H),
20.88, 18.12,







1.27-1.15 (m, 1H)
17.30


F234
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.36 (d, J = 7.9 Hz,
(CDCl3) δ






[M + H]+
1H), 8.26 (d, J = 5.4 Hz,
176.27,






calcd for
1H),
175.58,






C33H43N2O10,
7.30-7.20 (m, 2H),
172.67,






627.2912;
6.99-6.91 (m, 2H), 6.87 (d, J = 7.8 Hz,
162.97,






found,
2H), 5.77 (d, J = 1.2 Hz,
160.27,






627.2919
2H),
157.81,







5.39 (dd, J = 9.7, 7.9 Hz,
145.56,







1H), 5.09 (dq, J = 9.9,
144.31,







6.4 Hz, 1H), 4.68 (dt,
141.91,







J = 10.7, 7.5 Hz, 1H),
129.46,







4.40 (dd, J = 6.7, 4.8 Hz,
121.43,







1H), 3.89 (s, 3H),
116.50,







2.56 (tt, J = 14.0, 7.2 Hz,
109.60, 89.89,







2H), 2.41 (dt, J = 13.8,
79.80, 74.96,







7.1 Hz, 1H),
71.16, 56.14,







2.31-2.17 (m, 1H),
51.63, 43.74,







2.01-1.85 (m, 1H),
33.85, 33.23,







1.80-1.46 (m, 9H),
29.84, 29.72,







1.43-1.28 (m, 4H),
28.94, 25.70,







1.22 (dd, J = 16.1, 7.5 Hz,
25.61, 18.68,







1H), 1.15 (d, J = 7.0 Hz,
18.12, 17.30







6H)



F235
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.51 (d, J = 7.6 Hz,
(CDCl3) δ






[M + H]+
1H), 8.33 (d, J = 5.4 Hz,
175.57,






calcd for
1H),
172.56,






C30H37N2O9,
7.28-7.19 (m, 2H), 7.00 (d, J = 5.5 Hz,
168.89,






569.2429;
1H), 6.94 (t, J = 7.4 Hz,
162.42,






found,
1H),
159.47,






569.2427
6.89-6.82 (m, 2H),
157.81,







5.37 (dd, J = 9.8, 7.9 Hz,
146.67,







1H), 5.09 (dq, J = 9.9,
141.32,







6.4 Hz, 1H), 4.68 (dt,
137.55,







J = 10.6, 7.7 Hz, 1H),
129.47,







4.39 (ddd, J = 7.5, 5.5,
121.44,







1.7 Hz, 1H), 3.90 (s,
116.50,







3H), 2.64-2.52 (m,
109.86, 79.80,







1H), 2.40 (s, 4H),
74.94, 71.21,







2.30-2.16 (m, 1H),
56.30, 51.34,







1.98-1.83 (m, 1H),
43.74, 33.48,







1.78-1.45 (m, 9H),
29.84, 29.73,







1.39-1.28 (m, 4H),
28.99, 25.70,







1.24-1.13 (m, 1H)
25.61, 20.75,








18.09, 17.28


F236
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.47 (d, J = 8.0 Hz,
(CDCl3) δ






[M + H]+
1H), 8.32 (d, J = 5.4 Hz,
175.58,






calcd for
1H),
172.64,






C32H39N2O9,
7.26-7.20 (m, 2H), 6.99 (d, J = 5.5 Hz,
172.46,






595.2650;
1H), 6.94 (t, J = 7.3 Hz,
162.36,






found,
1H), 6.86 (d,
159.52,






595.2657
J = 7.8 Hz, 2H),
157.82,







5.37 (dd, J = 9.8, 7.9 Hz,
146.58,







1H), 5.08 (dq, J = 9.8,
141.70,







6.4 Hz, 1H), 4.72 (dt,
137.51,







J = 10.6, 7.7 Hz, 1H),
129.46,







4.39 (ddd, J = 7.5, 5.4,
121.43,







1.7 Hz, 1H), 3.90 (s,
116.51,







3H), 2.66-2.53 (m,
109.75, 79.82,







1H), 2.40 (dt, J = 13.9,
74.96, 71.15,







7.2 Hz, 1H),
56.32, 51.25,







2.31-2.15 (m, 1H),
43.74, 33.56,







2.02-1.84 (m, 2H),
29.84, 29.73,







1.79-1.46 (m, 9H),
29.00, 25.70,







1.32 (t, J = 6.9 Hz,
25.61, 18.10,







4H), 1.27-1.16 (m,
17.28, 13.00,







3H), 1.07 (dq, J = 7.2,
9.32







3.7 Hz, 2H)



F237
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.32 (d, J = 7.9 Hz,
(CDCl3) δ






[M + H]+
1H), 8.27 (d, J = 5.4 Hz,
175.58,






calcd for
1H), 7.25 (dd, J = 8.6,
172.64,






C33H43N2O11,
7.4 Hz, 2H),
170.09,






643.2861;
6.98-6.91 (m, 2H),
162.94,






found,
6.90-6.83 (m, 2H), 5.82 (s,
160.20,






643.2874
2H), 5.39 (dd, J = 9.8,
157.80,







7.9 Hz, 1H), 5.09 (dq,
145.75,







J = 9.8, 6.4 Hz, 1H),
144.05,







4.67 (dt, J = 10.7, 7.5 Hz,
142.10,







1H), 4.39 (ddd, J = 7.5,
129.47,







5.4, 1.8 Hz,
121.44,







1H), 4.10 (s, 2H),
116.50,







3.90 (s, 3H), 3.60 (q, J = 7.0 Hz,
109.76, 89.53,







2H),
79.80, 74.95,







2.59 (ddd, J = 15.6, 8.3, 7.1 Hz,
71.20, 67.79,







1H), 2.40 (dt, J = 13.8,
67.19, 56.23,







7.1 Hz, 1H),
51.62, 43.74,







2.32-2.16 (m, 1H),
33.22, 29.84,







2.01-1.85 (m, 1H),
29.73, 28.94,







1.80-1.46 (m, 9H),
25.70, 25.61,







1.43-1.30 (m, 4H),
18.11, 17.30,







1.23 (t, J = 7.0 Hz,
15.02







4H)



F238
White Solid
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
7.26 (t, J = 7.9 Hz,
(CDCl3) δ






[M + H]+
2H), 6.96 (t, J = 7.3 Hz,
174.04,






calcd for
1H), 6.87 (d, J = 8.1 Hz,
169.82,






C19H26NO5,
2H), 5.34 (dd,
157.67,






348.1805;
J = 9.4, 8.1 Hz, 1H),
129.50,






found,
5.06 (dt, J = 12.7, 6.3 Hz,
121.67,






348.1807
1H),
116.61, 79.54,







4.47-4.32 (m, 1H), 4.01 (dd, J = 10.3,
74.92, 72.49,







7.6 Hz, 1H),
51.72, 30.78,







2.39 (ddt, J = 100.3,
28.74, 17.49,







15.5, 7.2 Hz, 5H),
17.05, 12.75,







1.94-1.67 (m, 2H),
8.63, 8.55







1.61 (q, J = 11.4 Hz,








1H), 1.49 (tt, J = 8.1,








4.6 Hz, 1H), 1.35 (d, J = 6.3 Hz,








3H),








1.13 (dd, J = 16.1, 6.9 Hz,








1H), 0.98-0.69 (m,








4H)



F239
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






m/z
12.03 (s, 1H), 8.45 (d,
(CDCl3) δ






[M + H]+
J = 8.0 Hz, 1H),
173.88,






calcd for
7.99 (d, J = 5.2 Hz, 1H),
172.07,






C26H31N2O8,
7.33-7.17 (m, 2H),
168.70,






499.2075;
7.01-6.93 (m, 1H),
157.85,






found,
6.92-6.84 (m, 3H),
155.39,






499.2077
5.38 (dd, J = 9.7, 7.8 Hz,
148.77,







1H), 5.11 (dq, J = 9.8,
140.54,







6.4 Hz, 1H),
130.31,







4.67 (dt, J = 10.7, 7.6 Hz,
129.49,







1H), 4.41 (ddd, J = 7.6,
121.56,







5.5, 1.9 Hz, 1H),
116.69,







3.94 (s, 3H), 2.41 (dt,
109.53, 79.72,







J = 13.7, 7.1 Hz, 1H),
75.19, 71.52,







2.33-2.19 (m, 1H),
56.09, 51.29,







2.01-1.86 (m, 1H),
33.16, 28.97,







1.75 (dt, J = 15.5, 7.7 Hz,
18.04, 17.25,







1H),
12.81, 8.58,







1.55-1.44 (m, 1H), 1.41 (d, J = 12.9 Hz,
8.50







1H), 1.35 (d,








J = 6.4 Hz, 3H),








1.28-1.17 (m, 1H),








0.99-0.72 (m, 4H)



F240
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






m/z
8.31 (d, J = 7.9 Hz,
(CDCl3) δ






[M + H]+
1H), 8.27 (d, J = 5.4 Hz,
173.86,






calcd for
1H),
172.66,






C29H35N2O10,
7.30-7.21 (m, 2H),
170.29,






571.2286;
6.99-6.92 (m, 2H),
162.99,






found,
6.92-6.87 (m, 2H), 5.74 (s, 2H),
160.29,






571.2298
5.37 (dd, J = 9.7, 7.9 Hz,
157.90,







1H), 5.09 (dq, J = 9.8,
145.71,







6.4 Hz, 1H),
144.08,







4.68 (dt, J = 10.7, 7.5 Hz,
142.24,







1H), 4.40 (ddd, J = 7.6,
129.46,







5.6, 1.8 Hz, 1H),
121.50,







3.91 (s, 3H), 2.41 (dt,
116.69,







J = 13.7, 7.1 Hz, 1H),
109.68, 89.52,







2.31-2.17 (m, 1H),
79.76, 75.29,







2.07 (s, 3H),
71.22, 56.20,







1.99-1.85 (m, 1H),
51.65, 33.20,







1.72 (dq, J = 15.7, 7.8 Hz,
29.11, 20.87,







1H), 1.49 (tt, J = 8.0,
18.14, 17.25,







4.6 Hz, 1H), 1.34 (d, J = 6.4 Hz,
12.81, 8.53,







4H),
8.46







1.29-1.16 (m, 1H),








0.97-0.70 (m, 4H)



F241
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.36 (d, J = 7.9 Hz,
(CDCl3) δ






[M + H]+
1H), 8.26 (d, J = 5.4 Hz,
176.26,






calcd for
1H),
173.87,






C31H39N2O10,
7.29-7.21 (m, 2H),
172.66,






599.2599;
6.99-6.92 (m, 2H), 6.89 (dd, J = 8.7,
162.97,






found,
1.0 Hz, 2H),
160.27,






599.2596
5.77 (d, J = 1.3 Hz, 2H),
157.91,







5.37 (dd, J = 9.8, 7.8 Hz,
145.57,







1H), 5.09 (dq, J = 9.8,
144.30,







6.4 Hz, 1H),
141.91,







4.68 (dt, J = 10.7, 7.5 Hz,
129.46,







1H), 4.40 (ddd, J = 7.6,
121.49,







5.6, 1.8 Hz, 1H),
116.68,







3.89 (s, 3H),
109.61, 89.88,







2.55 (hept, J = 7.0 Hz, 1H),
79.75, 75.29,







2.41 (dt, J = 13.7, 7.1 Hz,
71.21, 56.15,







1H), 2.24 (ddt, J = 13.2,
51.65, 33.85,







9.5, 7.5 Hz, 1H),
33.21, 29.11,







2.00-1.83 (m, 1H),
18.68, 18.14,







1.72 (dq, J = 15.7, 7.9 Hz,
17.25, 12.81,







1H),
8.53, 8.46







1.55-1.45 (m, 1H), 1.34 (d, J = 6.4 Hz,








4H),








1.22 (ddd, J = 19.3, 7.3, 5.1 Hz,








1H), 1.14 (d, J = 7.0 Hz,








6H),








0.96-0.71 (m, 4H)



F242
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13CC NMR






(m/z)
8.51 (d, J = 7.6 Hz,
(CDCl3) δ






[M + H]+
1H), 8.33 (d, J = 5.4 Hz,
173.86,






calcd for
1H),
172.56,






C28H33N2O9,
7.29-7.22 (m, 2H), 7.00 (d, J = 5.5 Hz,
168.89,






541.2181;
1H), 6.95 (t, J = 7.3 Hz,
162.41,






found,
1H), 6.88 (d,
159.47,






541.2185
J = 8.0 Hz, 2H),
157.91,







5.35 (dd, J = 9.7, 7.8 Hz,
146.68,







1H), 5.08 (dq, J = 9.8,
141.32,







6.4 Hz, 1H), 4.67 (dt,
137.55,







J = 10.5, 7.7 Hz, 1H),
129.46,







4.44-4.34 (m, 1H),
121.50,







3.90 (s, 3H), 2.40 (s,
116.68,







4H), 2.32-2.16 (m,
109.86, 79.75,







1H), 1.96-1.82 (m,
75.28, 71.25,







1H), 1.71 (dt, J = 15.5,
56.30, 51.36,







8.0 Hz, 1H),
33.46, 29.16,







1.48 (tt, J = 8.1, 4.6 Hz,
20.74, 18.11,







1H), 1.34 (t, J = 7.6 Hz,
17.23, 12.80,







4H),
8.53, 8.47







1.27-1.15 (m, 1H),








0.97-0.69 (m, 4H)



F243
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.49 (d, J = 7.1 Hz,
(CDCl3) δ






[M + H]+
1H), 8.32 (d, J = 5.4 Hz,
173.87,






calcd for
1H),
172.55,






C30H37N2O10,
7.30-7.22 (m, 2H), 6.99 (d, J = 5.5 Hz,
169.43,






585.2443;
1H),
162.36,






found,
6.98-6.93 (m, 1H),
159.47,






585.2447
6.91-6.86 (m, 2H),
157.90,







5.35 (dd, J = 9.8, 7.8 Hz,
146.73,







1H), 5.08 (dq, J = 9.8,
141.34,







6.4 Hz, 1H), 4.67 (dt,
137.39,







J = 10.6, 7.6 Hz, 1H),
129.46,







4.39 (ddd, J = 7.6, 5.6,
121.50,







1.8 Hz, 1H), 3.89 (s,
116.68,







3H), 3.81 (t, J = 6.6 Hz,
109.87, 79.77,







2H), 3.41 (s, 3H),
75.27, 71.22,







2.98 (t, J = 6.6 Hz,
67.57, 58.78,







2H), 2.38 (dt, J = 13.8,
56.33, 51.33,







7.1 Hz, 1H),
34.63, 33.45,







2.23 (ddt, J = 13.3,
29.12, 18.11,







9.5, 7.5 Hz, 1H),
17.22, 12.80,







1.96-1.83 (m, 1H),
8.53, 8.46







1.70 (dq, J = 15.6, 7.8 Hz,








1H), 1.48 (tt, J = 8.0,








4.6 Hz, 1H),








1.40-1.27 (m, 4H),








1.21 (ddd, J = 16.0, 6.2, 2.2 Hz,








1H),








0.96-0.70 (m, 4H)



F244
White Solid
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.61 (s, 3H),
(CDCl3) δ






[M + H]+
3.56-3.51 (m, 1H),
170.09,






calcd for
2.59-2.47 (m, 1H),
142.36,






C14H26NO4,
2.20-1.98 (m, 1H), 1.70 (d,
112.26, 85.41,






272.1862;
J = 45.2 Hz, 4H),
82.94, 73.77,






found,
1.57 (d, J = 3.2 Hz, 1H),
72.99, 61.47,






272.1856
1.40 (d, J = 6.2 Hz,
52.24, 30.89,







3H), 0.96-0.78 (m,
29.38, 27.77,







1H), 4.87-4.82 (m,
19.55, 17.66







0H), 4.97 (s, 1H),








4.87 (s, 1H), 4.73 (dq, J = 12.4,








6.0 Hz, 1H),








4.11-4.01 (m, 1H),








3.95 (d, J = 12.1 Hz,








1H), 3.84 (d, J = 12.1 Hz,








1H), 3.57 (s, 3H),








3.47-3.34 (m, 1H),








3.29-3.21 (m, 1H)



F245
Off-White
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Foam


(m/z)
12.07 (dd, J = 4.6, 0.5 Hz,
(CDCl3) δ






[M + Na]+
1H), 8.47 (d, J = 8.1 Hz,
171.97,






calcd for
1H), 7.99 (d, J = 5.2 Hz,
168.66,






C21H30N2NaO7,
1H), 6.87 (d,
155.34,






445.1945;
J = 5.2 Hz, 1H),
148.72,






found,
4.99 (dd, J = 2.0, 0.9 Hz,
142.47,






445.1961
1H), 4.91-4.86 (m,
140.51,







1H), 4.80 (dq, J = 9.5,
130.38,







6.4 Hz, 1H), 4.59 (dt,
112.18,







J = 10.8, 7.6 Hz, 1H),
109.48, 85.65,







3.98 (d, J = 12.1 Hz,
83.14, 73.10,







1H), 3.94 (s, 3H),
73.07, 61.48,







3.87 (d, J = 12.1 Hz, 1H),
56.06, 51.28,







3.59 (s, 3H),
33.33, 27.87,







3.42 (ddd, J = 7.0, 5.2, 1.7 Hz,
19.56, 18.24,







1H), 3.32 (dd, J = 9.5,
17.74







7.4 Hz, 1H),








2.38 (ddd, J = 13.9, 10.1,








4.2 Hz, 1H),








2.24-2.06 (m, 1H), 1.78 (s,








2H), 1.73-1.63 (m,








2H), 1.59 (d, J = 2.3 Hz,








1H),








1.47-1.33 (m, 4H),








1.01-0.89 (m, 1H)



F246
White Solid
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.67 (s, 3H), 4.73 (dq,
(CDCl3) δ






[M + Na]+
J = 12.7, 6.2 Hz, 1H),
170.05, 85.36,






calcd for
4.11-3.96 (m, 1H),
83.85, 75.84,






C14H27NNaO4,
3.55 (s, 3H),
73.76, 61.34,






296.1832;
3.35-3.17 (m, 3H),
52.22, 31.02






found,
3.11 (dd, J = 8.7, 6.4 Hz,
28.83, 27.72,






296.1832
1H), 2.52 (d, J = 6.8 Hz,
19.46, 19.45,







1H), 2.12 (dd, J = 15.4,
17.79, 17.71







5.7 Hz, 1H),








1.79 (ddd, J = 28.0,








13.9, 8.7 Hz, 2H),








1.61 (d, J = 7.3 Hz,








2H), 1.39 (d, J = 6.3 Hz,








3H), 0.92 (d, J = 2.7 Hz,








3H), 0.90 (d, J = 2.7 Hz,








3H),








0.87-0.76 (m, 1H)



F247
Off-White
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Solid


(m/z)
12.09 (s, 1H), 8.47 (d,
(CDCl3) δ






[M + Na]+
J = 8.1 Hz, 1H),
172.00,






calcd for
7.99 (d, J = 5.2 Hz, 1H),
168.65,






C21H32N2NaO7,
6.87 (d, J = 5.2 Hz,
155.34,






447.2102;
1H), 4.79 (dq, J = 9.3,
148.72,






found,
6.4 Hz, 1H), 4.59 (dt,
140.51,






447.2115
J = 10.8, 7.7 Hz, 1H),
130.39,







3.94 (s, 3H), 3.58 (s,
109.47, 85.55,







3H), 3.38-3.22 (m,
84.03, 75.91,







3H), 3.14 (dd, J = 8.7,
73.06, 61.37,







6.4 Hz, 1H), 2.37 (dt,
56.06, 51.29,







J = 13.9, 6.3 Hz, 1H),
33.34, 28.85,







2.22-2.06 (m, 1H),
27.75, 19.48,







1.84 (dp, J = 13.2, 6.6 Hz,
19.46, 18.20,







1H), 1.69 (dd, J = 13.1,
17.79







6.0 Hz, 2H),








1.47-1.28 (m, 4H),








0.93 (d, J = 2.7 Hz,








3H), 0.92 (d, J = 2.7 Hz,








3H), 0.89 (d, J = 7.3 Hz,








1H)



F248
White Solid
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.66 (s, 3H),
(CDCl3) δ






[M + H]+
7.34-7.20 (m, 2H),
170.01,






calcd for
7.02-6.84 (m, 3H),
157.46,






C16H24NO4,
4.83 (dd, J = 9.4, 6.3 Hz,
129.57,






294.1700;
1H), 4.38-4.25 (m,
121.36,






found,
1H), 4.11 (s, 1H),
116.47, 84.83,






294.1716
3.58-3.41 (m, 4H),
82.64, 73.53,







2.50 (s, 1H),
61.41, 52.20,







2.29-2.06 (m, 1H), 1.68 (dd, J = 23.6,
30.82, 28.31,







12.8 Hz, 3H),
17.78, 17.73







1.43 (d, J = 6.2 Hz,








3H), 0.97 (dd, J = 15.6,








6.7 Hz, 1H)



F249
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
12.06 (d, J = 0.5 Hz,
(CDCl3) δ






[M + Na]+
1H), 8.46 (d, J = 8.1 Hz,
171.92,






calcd for
1H), 7.98 (d, J = 5.2 Hz,
168.69,






C23H28N2NaO7,
1H), 7.28 (dd,
157.57,






467.1789;
J = 8.2, 7.3 Hz, 2H),
155.36,






found,
7.01-6.90 (m, 3H),
148.74,






467.1810
6.86 (d, J = 5.2 Hz,
140.54,







1H), 4.91 (dq, J = 9.6,
130.35,







6.4 Hz, 1H), 4.64 (dt,
129.56,







J = 10.7, 7.7 Hz, 1H),
121.38,







4.40-4.32 (m, 1H),
116.64,







3.94 (s, 3H), 3.56 (s,
109.50, 85.04,







4H), 2.37 (dt, J = 13.6,
82.96, 72.83,







7.1 Hz, 1H),
61.43, 56.07,







2.19 (dddd, J = 15.8,
51.23, 33.21,







10.1, 8.0, 5.4 Hz, 1H),
28.29, 18.20,







1.90-1.76 (m, 1H),
17.82







1.75-1.58 (m, 1H),








1.47 (d, J = 6.4 Hz,








3H), 1.41-1.29 (m,








1H), 1.06 (dd, J = 16.1,








7.8 Hz, 1H)



F250
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.31 (d, J = 8.0 Hz,
(CDCl3) δ






[M + H]+
1H), 8.28 (d, J = 5.4 Hz,
172.58,






calcd for
1H), 6.95 (d, J = 5.4 Hz,
170.25,






C24H35N2O9,
1H), 5.74 (s,
162.96,






495.2337;
2H), 5.01-4.97 (m,
160.25,






found,
1H), 4.91-4.86 (m,
145.73,






495.2368
1H), 4.78 (dq, J = 9.5,
143.96,







6.4 Hz, 1H), 4.61 (dt,
142.50,







J = 10.8, 7.6 Hz, 1H),
142.39,







3.98 (d, J = 12.1 Hz,
112.15,







1H), 3.91 (s, 3H),
109.61, 89.51,







3.87 (d, J = 12.1 Hz, 1H),
85.69, 83.21,







3.59 (s, 3H), 3.41 (td,
73.03, 72.82,







J = 6.1, 5.1, 1.7 Hz,
61.46, 56.18,







1H), 3.31 (dd, J = 9.5,
51.60, 33.40,







7.3 Hz, 1H),
29.37, 27.92,







2.45-2.32 (m, 1H), 2.07 (s,
20.86, 19.56,







4H), 1.77 (s, 2H),
18.29, 17.73







1.68 (dq, J = 15.1, 8.4 Hz,








2H), 1.59 (d, J = 2.8 Hz,








1H), 1.40 (d, J = 6.4 Hz,








4H),








0.93 (ddd, J = 14.3, 7.4, 2.3 Hz,








1H)



F251
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.31 (d, J = 8.0 Hz,
(CDCl3) δ






[M + Na]+
1H), 8.27 (d, J = 5.4 Hz,
172.61,






calcd for
1H), 6.95 (d, J = 5.4 Hz,
170.25,






C24H36N2NaO9,
1H), 5.74 (s,
162.95,






519.2313;
2H), 4.77 (dq, J = 9.3,
160.25,






found,
6.4 Hz, 1H), 4.61 (dt,
145.72,






519.2336
J = 10.8, 7.5 Hz, 1H),
143.96,







3.91 (s, 3H), 3.58 (s,
142.41,







3H), 3.30 (ddt, J = 11.6,
109.60, 89.52,







9.3, 6.4 Hz, 3H),
85.59, 84.11,







3.13 (dd, J = 8.8, 6.4 Hz,
75.88, 72.78,







1H), 2.38 (dt, J = 13.8,
61.35, 56.18,







6.7 Hz, 1H),
51.61, 33.42,







2.07 (s, 4H),
28.84, 27.81,







1.89-1.77 (m, 1H),
20.86, 19.48,







1.75-1.58 (m, 2H),
19.46, 18.26,







1.44-1.30 (m, 4H), 0.93 (d,
17.77







J = 2.9 Hz, 3H),








0.92 (d, J = 2.9 Hz, 3H),








0.88 (d, J = 7.4 Hz,








1H)



F252
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.31 (d, J = 8.0 Hz,
(CDCl3) δ






[M + Na]+
1H), 8.27 (d, J = 5.4 Hz,
172.53,






calcd for
1H),
170.27,






C26H32N2NaO9,
7.31-7.24 (m, 2H),
163.00,






540.2032;
6.98-6.92 (m, 4H), 5.74 (s, 2H),
160.27,






found,
4.89 (dq, J = 9.6, 6.4 Hz,
157.62,






540.2042
1H), 4.66 (dt, J = 10.7,
145.74,







7.6 Hz, 1H),
144.00,







4.40-4.32 (m, 1H),
142.34,







3.90 (s, 3H), 3.55 (s,
129.53,







4H), 2.37 (dt, J = 13.6,
121.32,







7.1 Hz, 1H),
116.65,







2.17 (ddddd, J = 15.9,
109.64, 89.51,







13.3, 10.3, 8.1, 2.7 Hz,
85.09, 83.05,







1H), 2.07 (s, 3H),
72.54, 61.42,







1.88-1.76 (m, 1H),
56.19, 51.57,







1.64 (dq, J = 15.5, 7.7 Hz,
33.28, 28.36,







1H), 1.45 (d, J = 6.4 Hz,
20.88, 18.27,







3H),
17.81







1.37-1.25 (m, 1H),








1.05 (dd, J = 16.1, 7.8 Hz,








1H)



F253
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.37 (d, J = 8.0 Hz,
(CDCl3) δ






[M + Na]+
1H), 8.27 (d, J = 5.4 Hz,
176.22,






calcd for
1H), 6.94 (d, J = 5.4 Hz,
172.58,






C26H38N2NaO9,
1H),
162.94,






545.2470;
5.81-5.73 (m, 2H),
160.24,






found,
5.01-4.96 (m, 1H),
145.59,






545.2500
4.91-4.86 (m, 1H),
144.19,







4.78 (dq, J = 9.5, 6.4 Hz,
142.50,







1H), 4.61 (dt, J = 10.7,
142.06,







7.6 Hz, 1H),
112.14,







3.98 (d, J = 12.1 Hz,
109.54, 89.88,







1H), 3.89 (s, 4H),
85.70, 83.22,







3.59 (s, 3H), 3.41 (ddd, J = 6.9,
73.03, 72.81,







5.2, 1.7 Hz, 1H),
61.46, 56.13,







3.31 (dd, J = 9.5, 7.3 Hz,
51.60, 33.84,







1H), 2.55 (hept, J = 7.0 Hz,
33.42, 29.37,







1H),
27.92, 19.57,







2.43-2.32 (m, 1H),
18.67, 18.30,







2.12 (dddd, J = 15.8, 13.7,
17.73







6.9, 4.2 Hz, 1H),








1.77 (s, 2H), 1.68 (dq, J = 15.1,








8.3 Hz, 2H),








1.59 (d, J = 2.7 Hz,








1H), 1.41 (d, J = 6.4 Hz,








3H),








1.39-1.28 (m, 1H), 1.15 (s, 3H),








1.14 (s, 3H),








1.02-0.88 (m, 1H)



F254
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.37 (d, J = 8.1 Hz,
(CDCl3) δ






[M + Na]+
1H), 8.27 (d, J = 5.4 Hz,
176.22,






calcd for
1H), 6.94 (d, J = 5.4 Hz,
172.60,






C26H40N2NaO9,
1H),
162.93,






547.2626;
5.81-5.73 (m, 2H),
160.24,






found,
4.77 (dq, J = 9.3, 6.4 Hz,
145.59,






547.2648
1H), 4.61 (dt, J = 10.8,
144.18,







7.5 Hz, 1H),
142.08,







3.89 (s, 3H), 3.58 (s,
109.53, 89.89,







3H), 3.30 (ddt, J = 11.7,
85.60, 84.11,







9.3, 6.4 Hz, 3H),
75.88, 72.76,







3.13 (dd, J = 8.8, 6.4 Hz,
61.35, 56.12,







1H), 2.55 (hept, J = 7.0 Hz,
51.61, 33.84,







1H),
33.44, 28.84,







2.37 (dt, J = 13.8, 6.7 Hz,
27.82, 19.48,







1H), 2.12 (dddd, J = 15.7,
19.47, 18.67,







10.1, 8.3, 5.2 Hz,
18.27, 17.77







1H),








1.91-1.76 (m, 1H),








1.75-1.56 (m, 2H), 1.40 (d, J = 6.4 Hz,








3H),








1.38-1.27 (m, 1H), 1.14 (d,








J = 7.0 Hz, 6H),








0.93 (d, J = 3.0 Hz, 3H),








0.92 (d, J = 3.0 Hz,








3H), 0.89 (dt, J = 7.8,








1.9 Hz, 1H)



F255
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.37 (d, J = 8.0 Hz,
(CDCl3) δ






[M + Na]+
1H), 8.26 (d, J = 5.4 Hz,
176.23,






calcd for
1H),
172.53,






C28H36N2NaO9,
7.33-7.23 (m, 2H),
162.97,






567.2313;
7.01-6.91 (m, 4H),
160.25,






found,
5.81-5.73 (m, 2H), 4.89 (dq, J = 9.6,
157.63,






567.2346
6.4 Hz, 1H),
145.60,







4.65 (dt, J = 10.7, 7.6 Hz,
144.22,







1H), 4.39-4.32 (m,
142.01,







1H), 3.88 (s, 3H),
129.53,







3.55 (s, 4H), 2.55 (hept, J = 7.0 Hz,
121.32,







1H), 2.37 (dt,
116.65,







J = 13.6, 7.0 Hz, 1H),
109.58, 89.88,







2.17 (dddd, J = 15.7,
85.09, 83.05,







10.1, 8.0, 5.4 Hz, 1H),
72.53, 61.42,







1.87-1.78 (m, 1H),
56.14, 51.57,







1.64 (dq, J = 15.5, 7.7 Hz,
33.86, 33.29,







1H), 1.45 (d, J = 6.4 Hz,
28.36, 18.68,







3H),
18.28, 17.81







1.37-1.28 (m, 1H), 1.14 (d,








J = 7.0 Hz, 6H),








1.06 (dd, J = 16.1, 7.8 Hz,








1H)



F256
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.52 (d, J = 6.9 Hz,
(CDCl3) δ






[M + H]+
1H), 8.33 (d, J = 5.4 Hz,
172.46,






calcd for
1H), 7.00 (d, J = 5.5 Hz,
168.86,






C23H33N2O8,
1H),
162.38,






465.2231;
5.00-4.96 (m, 1H),
159.43,






found,
4.90-4.86 (m, 1H),
146.69,






465.2246
4.77 (dq, J = 9.5, 6.4 Hz,
142.49,







1H), 4.60 (dt, J = 10.7,
141.38,







7.7 Hz, 1H),
137.48,







3.98 (d, J = 12.1 Hz,
112.19,







5H), 3.58 (s, 3H),
109.81, 85.67,







3.41 (ddd, J = 7.0, 5.2, 1.7 Hz,
83.21, 73.04,







1H), 3.29 (dd, J = 9.5,
72.84, 61.46,







7.3 Hz, 1H),
56.28, 51.33,







2.40 (s, 4H), 2.11 (dddd, J = 15.7,
29.37, 27.93,







10.1, 8.5, 5.3 Hz,
20.73, 19.57,







1H), 1.77 (s, 2H),
18.26, 17.72







1.72-1.61 (m, 2H),








1.59 (d, J = 3.0 Hz,








1H), 1.39 (d, J = 6.4 Hz,








3H), 1.32 (qd, J = 10.9,








5.2 Hz, 1H),








0.97-0.87 (m, 1H)



F257
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.52 (d, J = 7.2 Hz,
(CDCl3) δ






[M + H]+
1H), 8.32 (d, J = 5.4 Hz,
172.48,






calcd for
1H), 7.00 (d, J = 5.5 Hz,
168.85,






C23H35N2O8,
1H), 4.76 (dq,
162.37,






467.2388;
J = 9.4, 6.4 Hz, 1H),
159.42,






found,
4.59 (dt, J = 10.7, 7.6 Hz,
146.69,






467.2414
1H), 3.90 (s, 3H),
141.39,







3.57 (s, 3H),
137.47,







3.35-3.22 (m, 3H),
109.80, 85.57,







3.13 (dd, J = 8.8, 6.4 Hz,
84.10, 75.89,







1H), 2.40 (s, 4H),
72.79, 61.33,







2.11 (tdd, J = 13.8, 6.6, 4.1 Hz,
56.27, 51.33,







1H), 1.83 (dp, J = 13.2,
33.62, 28.83,







6.6 Hz, 1H),
27.83, 20.73,







1.71-1.58 (m, 2H)
19.47, 18.22,







1.38 (d, J = 6.4 Hz,
17.75







3H), 1.36-1.24 (m,








1H), 0.93 (d, J = 3.4 Hz,








3H), 0.91 (d, J = 3.4 Hz,








3H), 0.87 (d, J = 7.4 Hz,








1H)



F258
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.52 (d, J = 6.9 Hz,
(CDCl3) δ






[M + H]+
1H), 8.32 (d, J = 5.4 Hz,
172.41,






calcd for
1H),
168.88,






C25H31N2O8,
7.31-7.25 (m, 2H),
162.43,






487.2075;
7.01-6.93 (m, 4H), 4.88 (dq, J = 9.6,
159.45,






found,
6.4 Hz, 1H),
157.63,






487.2095
4.64 (dt, J = 10.7, 7.6 Hz,
146.71,







1H), 4.38-4.31 (m,
141.34,







1H), 3.89 (s, 3H),
137.51,







3.55 (s, 3H),
129.54,







3.54-3.50 (m, 1H), 2.40 (s, 3H),
121.33,







2.39-2.30 (m, 1H),
116.65,







2.22-2.09 (m, 1H),
109.84, 85.07,







1.86-1.74 (m, 1H),
83.05, 72.56,







1.62 (dq, J = 15.3, 7.8 Hz,
61.42, 56.30,







1H), 1.44 (d, J = 6.4 Hz,
51.29, 33.50,







3H),
28.39, 20.75,







1.35-1.21 (m, 1H),
18.24, 17.80







1.04 (dd, J = 16.1, 7.8 Hz,








1H)



F259
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.49 (s, 1H), 8.33 (d, J = 5.5 Hz,
(CDCl3) δ






[M + H]+
1H), 7.00 (d,
172.51,






calcd for
J = 5.5 Hz, 1H),
169.44,






C25H39N2O9,
4.76 (dq, J = 9.4, 6.4 Hz,
162.33,






511.2681;
1H), 4.58 (dt, J = 10.7,
159.43,






found,
7.8 Hz, 1H),
146.74,






511.2650
3.90 (s, 3H), 3.81 (t, J = 6.6 Hz,
141.43,







2H), 3.57 (s,
137.32,







3H), 3.41 (s, 3H),
109.77, 85.57,







3.35-3.23 (m, 3H),
84.11, 75.89,







3.13 (dd, J = 8.8, 6.4 Hz,
72.79, 67.57,







1H), 2.99 (t, J = 6.6 Hz,
61.37, 58.80,







2H), 2.34 (dt, J = 13.8,
56.32, 51.31,







6.6 Hz, 1H),
34.61, 33.63,







2.19-2.02 (m, 1H)
28.83, 27.79,







1.83 (dp, J = 13.2, 6.6 Hz,
19.48, 18.22,







1H),
17.76







1.70-1.61 (m, 2H), 1.38 (d, J = 6.4 Hz,








3H),








1.36-1.24 (m, 1H), 0.93 (d,








J = 3.4 Hz, 3H),








0.91 (d, J = 3.4 Hz, 3H),








0.87 (d, J = 7.4 Hz,








1H)



F260
White Foam
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.50 (s, 1H), 8.33 (d, J = 5.4 Hz,
(CDCl3) δ






[M + H]+
1H),
172.42,






calcd for
7.30-7.26 (m, 2H),
169.44,






C27H35N2O9,
7.02-6.91 (m, 4H),
162.37,






531.2350;
4.88 (dq, J = 9.7, 6.4 Hz,
159.44,






found,
1H), 4.64 (dt, J = 10.6,
157.60,






531.2337
7.8 Hz, 1H),
146.75,







4.35 (t, J = 5.5 Hz,
141.36,







1H), 3.90 (s, 3H),
137.34,







3.81 (t, J = 6.6 Hz, 2H),
129.53,







3.55 (s, 4H), 3.41 (s,
121.33,







3H), 2.99 (t, J = 6.6 Hz,
116.65,







2H), 2.34 (dt, J = 13.7,
109.81, 85.04,







7.1 Hz, 1H),
83.05, 72.54,







2.23-2.09 (m, 1H),
67.57, 61.43,







1.85-1.74 (m, 1H),
58.80, 56.32,







1.60 (dd, J = 15.4, 8.5 Hz,
51.25, 34.61,







1H), 1.44 (d, J = 6.4 Hz,
33.48, 28.33,







3H), 1.28 (q, J = 11.3 Hz,
18.22, 17.78







1H),








1.04 (dd, J = 16.1, 7.8 Hz,








1H)



F261
White Solid
—
IR
HRMS-ESI
—
19F NMR





(Thin
(m/z)

(CDCl3) δ −122.90





Film)
[M]+







3449,
calcd for







2950,
C18H26FNO4,







2900,
339.1846;







1743,
found,







1713,
339.1851







1504,








1203





F262
Fluffy White
—
—
HRMS-ESI
1H NMR (CDCl3) δ
19F NMR



Solid


(m/z)
12.06 (d, J = 0.6 Hz,
(CDCl3) δ −123.15






[M]+
1H), 8.48 (dd, J = 8.1,







calcd for
4.4 Hz, 1H), 7.98 (dd,







C25H31FN2O7,
J = 5.2, 4.4 Hz, 1H),







490.2115;
7.10-6.83 (m, 5H),







found,
5.02 (dq, J = 9.6, 6.4 Hz,







490.2114
1H), 4.62 (ddd, J = 10.8,








8.0, 7.2 Hz,








1H), 4.35-4.22 (m,








1H), 3.93 (s, 3H),








3.55 (ddd, J = 7.3, 5.3, 1.8 Hz,








1H), 3.46 (dt, J = 9.0,








6.6 Hz, 1H),








3.23 (dt, J = 9.0, 6.5 Hz,








1H), 2.47-2.31 (m,








1H), 2.29-2.09 (m,








1H), 1.87-1.68 (m,








2H), 1.58-1.39 (m,








3H), 1.37 (d, J = 6.4 Hz,








3H), 1.04 (ddt, J = 16.1,








6.6, 2.0 Hz, 1H),








0.79 (t, J = 7.4 Hz,








3H)



F263
White Solid
—
—
ESIMS
—
—






m/z 340








([M + H]+)




F264
White Solid
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
12.05 (d, J = 0.6 Hz,
(CDCl3) δ






[M]+
1H), 8.46 (d, J = 8.2 Hz,
171.93,






calcd for
1H), 7.98 (d, J = 5.2 Hz,
168.69,






C25H31FN2O7,
1H),
158.77,






490.2116;
7.02-6.83 (m, 5H),
155.36,






found,
4.91 (dq, J = 9.6, 6.4 Hz,
153.76 (d, J = 2.5 Hz),






490.2115
1H), 4.63 (ddd, J = 10.8,
148.73,







8.2, 7.2 Hz, 1H),
140.55,







4.26 (ddd, J = 7.1, 5.2,
130.33,







1.8 Hz, 1H), 3.94 (s,
118.01 (d, J = 7.9 Hz),







3H), 3.72 (dt, J = 9.0,
115.89 (d, J = 22.9 Hz),







6.5 Hz, 1H),
109.50, 84.31,







3.66-3.55 (m, 2H),
83.33, 75.69,







2.37 (ddd, J = 12.7, 7.6, 6.4 Hz,
73.01, 56.08,







1H),
51.21, 33.22,







2.20-2.02 (m, 1H),
28.24, 23.45,







1.89-1.75 (m, 1H),
18.19, 17.88,







1.74-1.59 (m, 1H),
10.61







1.61-1.44 (m, 5H),








1.43-1.27 (m, 1H), 1.04 (ddt, J = 16.1,








7.8, 1.8 Hz, 1H),








0.85 (t, J = 7.4 Hz,








3H)



F265
Colorless
—
—
HRMS-ESI
1H NMR (CDCl3) δ
19F NMR



Semi Solid


(m/z)
8.33 (d, J = 8.0 Hz,
(CDCl3) δ −123.28






[M]+calcd for
1H), 8.28 (d, J = 5.3 Hz,







C28H35FN2O9,
1H),







562.2327;
7.09-6.85 (m, 5H), 5.74 (s, 2H),







found,
5.00 (dq, J = 9.7, 6.4 Hz,







562.2330
1H), 4.64 (dq, J = 10.8,








7.9 Hz, 1H),








4.29 (dd, J = 9.6, 7.3 Hz,








1H), 3.91 (s, 3H),








3.54 (ddd, J = 7.2, 5.3,








1.8 Hz, 1H), 3.46 (dt,








J = 9.0, 6.6 Hz, 1H),








3.22 (dt, J = 8.9, 6.4 Hz,








1H), 2.42 (dtd, J = 13.5,








6.8, 6.2, 2.0 Hz,








1H), 2.20 (dddd, J = 15.9,








10.3, 8.4, 5.4 Hz,








1H), 2.07 (s, 3H),








1.82-1.69 (m, 2H),








1.48-1.38 (m, 3H),








1.35 (d, J = 6.4 Hz,








3H), 1.09-0.97 (m,








1H), 0.78 (t, J = 7.4 Hz,








3H)



F266
Colorless
—
—
HRMS-ESI
1H NMR (CDCl3) δ
19F NMR



Semi Solid


(m/z)
8.53 (d, J = 8.4 Hz,
(CDCl3) δ −123.29






[M]+
1H), 8.33 (dd, J = 5.5,







calcd for
4.3 Hz, 1H),







C27H33FN2O8,
7.09-6.84 (m, 5H),







532.2221;
4.99 (dq, J = 9.6, 6.4 Hz,







found,
1H), 4.62 (ddd, J = 10.7,







532.2227
8.4, 7.2 Hz, 1H),








4.27 (dd, J = 9.6, 7.3 Hz,








1H), 3.91 (s, 3H),








3.53 (ddd, J = 7.1, 5.3,








1.8 Hz, 1H), 3.45 (dt,








J = 9.0, 6.6 Hz, 1H),








3.22 (dt, J = 9.0, 6.5 Hz,








1H), 2.40 (s, 3H),








2.45-2.32 (m, 1H),








2.26-2.11 (m, 1H),








1.79-1.61 (m, 2H),








1.49-1.39 (m, 2H),








1.41-1.30 (m, 1H),








1.34 (d, J = 6.4 Hz,








3H), 1.08-0.96 (m,








1H), 0.78 (t, J = 7.4 Hz,








3H)



F267
White Solid
—
—
HRMS-ESI
1H NMR (600 MHz,
19F NMR






(m/z)
CDCl3) δ 8.31 (d, J = 8.0 Hz,
(CDCl3) δ −122.93






[M]+calcd for
1H), 8.27 (d, J = 5.4 Hz,







C28H35FN2O9,
1H),







562.2327;
6.99-6.92 (m, 3H),







found,
6.92-6.85 (m, 2H), 5.74 (s,







562.2335
2H), 4.89 (dq, J = 9.6,








6.4 Hz, 1H), 4.65 (dt,








J = 10.7, 7.6 Hz, 1H),








4.25 (ddd, J = 7.2, 5.3,








1.8 Hz, 1H), 3.91 (s,








3H), 3.72 (dt, J = 9.0,








6.5 Hz, 1H),








3.64-3.54 (m, 2H),








2.42-2.34 (m, 1H),








2.15-2.08 (m, 1H), 2.07 (s,








3H), 1.81 (dddd, J = 15.1,








11.9, 7.7, 1.6 Hz,








1H),








1.70-1.60 (m, 1H),








1.57-1.47 (m, 2H), 1.45 








(d, J = 6.4 Hz, 3H),








1.31 (dddd, J = 13.4, 12.0,








10.7, 1.4 Hz, 1H),








1.04 (ddt, J = 16.4,








8.0, 1.8 Hz, 1H),








0.84 (t, J = 7.4 Hz, 3H)



F268
White Solid
—
—
ESIMS
—
—






m/z 352








([M + H]+)




F269
White Solid
—
—
ESIMS
—
—






m/z 340








([M + H]+)




F270
White Solid
—
—
HRMS-ESI
1H NMR (600 MHz,
13C NMR (151 MHz,






(m/z)
CDCl3) δ 12.06 (d, J = 0.7 Hz,
CDCl3)






[M]+calcd for
1H), 8.48 (d, J = 8.2 Hz,
δ 171.99,






C26H34N2O8,
1H), 7.99 (d,
168.68,






502.2315;
J = 5.2 Hz, 1H),
155.37,






found,
7.06-7.00 (m, 2H),
154.24,






502.2317
6.93-6.84 (m, 1H),
154.00,







6.85-6.78 (m, 2H),
148.74,







5.01 (dq, J = 9.6, 6.4 Hz,
140.54,







1H), 4.66-4.57 (m,
130.37,







1H), 4.27 (dd, J = 9.6,
117.63,







7.3 Hz, 1H), 3.94 (s,
114.44,







3H), 3.78 (s, 3H),
109.50, 84.08,







3.55 (ddd, J = 7.2, 5.2, 1.7 Hz,
83.02, 72.94,







1H), 3.46 (dt, J = 9.0,
71.36, 56.08,







6.6 Hz, 1H),
55.69, 51.30,







3.27 (dt, J = 9.0, 6.5 Hz,
33.37, 28.03,







1H), 2.45-2.35 (m,
23.20, 18.30,







1H), 2.21 (dddd, J = 15.7,
18.19, 10.60







10.1, 8.3, 5.2 Hz,








1H), 1.76 (dddd, J = 14.8,








10.4, 7.2, 4.9 Hz,








2H), 1.51-1.40








(m, 3H), 1.38 (d, J = 6.4 Hz,








3H), 1.04 (ddt,








J = 16.1, 7.4, 1.9 Hz,








1H), 0.81 (t, J = 7.4 Hz,








3H)



F271
White Solid
—
—
HRMS-ESI
1H NMR (600 MHz,
19F NMR






(m/z)
CDCl3) δ 12.05 (s,
(CDCl3) δ −111.78






[M]+
1H), 8.47 (d, J = 8.1 Hz,







calcd for
1H), 8.00 (d, J = 5.2 Hz,







C25H31FN2O7,
1H), 7.21 (td,







490.2115;
J = 8.4, 6.8 Hz, 1H),







found,
6.89-6.82 (m, 3H),







490.2123
6.67 (tdd, J = 8.2, 2.3,








0.9 Hz, 1H), 5.03 (dq,








J = 9.6, 6.4 Hz, 1H),








4.62 (dt, J = 10.8, 7.7 Hz,








1H), 4.38 (dd, J = 9.6,








7.3 Hz, 1H),








3.94 (s, 3H), 3.55 (ddd, J = 7.3,








5.2, 1.7 Hz, 1H),








3.46 (dt, J = 9.0, 6.6 Hz,








1H), 3.22 (dt, J = 9.0,








6.4 Hz, 1H),








2.46-2.37 (m, 1H),








2.21 (dddd, J = 15.8, 10.1,








8.2, 5.2 Hz, 1H),








1.76 (dddd, J = 18.3, 12.9,








7.9, 3.7 Hz, 2H),








1.49-1.40 (m, 3H),








1.36 (d, J = 6.4 Hz, 3H),








1.05 (ddt, J = 16.1,








7.4, 1.9 Hz, 1H),








0.78 (t, J = 7.4 Hz, 3H)



F272
White Solid
—
—
HRMS-ESI
1H NMR (600 MHz,
13C NMR (151 MHz,






(m/z)
CDCl3) δ 12.05 (d, J = 0.7 Hz,
CDCl3)






[M]+
1H), 8.47 (d, J = 8.0 Hz,
δ 171.95,






calcd for
1H), 7.99 (d,
168.69,






C25H31ClN2O7,
J = 5.2 Hz, 1H),
160.39,






506.1820;
7.19 (t, J = 8.1 Hz, 1H),
155.38,






found,
7.14 (t, J = 2.2 Hz,
148.76,






506.1825
1H), 6.99-6.91 (m,
140.55,







2H), 6.87 (d, J = 5.2 Hz,
134.69,







1H), 5.03 (dq, J = 9.6,
130.35,







6.4 Hz, 1H),
130.09,







4.62 (dt, J = 10.8, 7.6 Hz,
121.59,







1H), 4.37 (dd, J = 9.6,
117.06,







7.2 Hz, 1H), 3.94 (s,
114.74,







3H), 3.55 (ddd, J = 7.2,
109.51, 83.28,







5.2, 1.8 Hz, 1H),
82.89, 72.50,







3.46 (dt, J = 9.0, 6.6 Hz,
71.26, 56.09,







1H), 3.21 (dt, J = 9.0,
51.29, 33.32,







6.4 Hz, 1H),
27.91, 23.15,







2.46-2.36 (m, 1H),
18.29, 18.07,







2.21 (dddd, J = 15.8, 10.2,
10.56







8.3, 5.2 Hz, 1H),








1.84-1.64 (m, 2H),








1.49-1.42 (m, 3H), 1.36 (d,








J = 6.4 Hz, 3H),








1.05 (ddt, J = 16.2, 7.6, 2.0 Hz,








1H), 0.79 (t, J = 7.4 Hz,








3H)



F273
White Solid
—
—
HRMS-ESI
1H NMR (600 MHz,
13C NMR (151 MHz,






(m/z)
CDCl3) δ 12.04 (d, J = 0.7 Hz,
CDCl3)






[M]+
1H), 8.47 (d, J = 8.1 Hz,
δ 171.94,






calcd for
1H), 7.99 (d,
168.69,






C25H31BrN2O7,
J = 5.2 Hz, 1H),
158.88,






550.1315;
7.39-7.33 (m, 2H),
155.38,






found,
7.01-6.95 (m, 2H), 6.87 (d,
148.76,






550.1320
J = 5.2 Hz, 1H),
140.55,







5.02 (dq, J = 9.5, 6.4 Hz,
132.19,







1H), 4.67-4.58 (m,
130.35,







1H), 4.34 (dd, J = 9.6,
118.27,







7.3 Hz, 1H), 3.94 (s,
113.52,







3H), 3.55 (ddd, J = 7.3,
109.52, 83.35,







5.2, 1.8 Hz, 1H),
82.88, 72.56,







3.45 (dt, J = 9.1, 6.6 Hz,
71.30, 56.09,







1H), 3.22 (dt, J = 9.0,
51.28, 33.32,







6.5 Hz, 1H),
27.95, 23.16,







2.45-2.36 (m, 1H),
18.28, 18.07,







2.21 (dddd, J = 15.8, 10.1,
10.57







8.4, 5.3 Hz, 1H),








1.75 (ttd, J = 15.3, 7.2, 5.3 Hz,








2H), 1.51-1.38








(m, 3H), 1.34 (d, J = 6.4 Hz,








3H), 1.04 (ddt,








J = 16.2, 7.2, 2.0 Hz,








1H), 0.78 (t, J = 7.4 Hz,








3H)



F274
Colorless
—
—
HRMS-ESI
1H NMR (600 MHz,
13C NMR (151 MHz,



Semi Solid


(m/z)
CDCl3) δ 8.53 (s, 1H),
CDCl3)






[M]+
8.33 (d, J = 5.4 Hz,
δ 172.49,






calcd for
1H), 7.06-7.01 (m,
168.90,






C28H36N2O9,
2H), 7.00 (d, J = 5.5 Hz,
162.41,






544.2421;
1H), 6.85-6.78
159.45,






found,
(m, 2H), 4.98 (dq, J = 9.5,
154.21,






544.2427
6.4 Hz, 1H),
154.04,







4.67-4.58 (m, 1H),
146.70,







4.25 (dd, J = 9.6, 7.3 Hz,
141.40,







1H), 3.90 (s, 3H),
137.51,







3.77 (s, 3H), 3.54 (ddd, J = 7.2,
117.64,







5.3, 1.8 Hz, 1H),
114.43,







3.45 (dt, J = 9.1, 6.7 Hz,
109.82, 84.14,







1H), 3.26 (dt, J = 9.1,
83.10, 72.68,







6.5 Hz, 1H),
71.34, 56.29,







2.39 (s, 3H),
55.69, 51.36,







2.39-2.34 (m, 1H),
33.67, 28.12,







2.23-2.13 (m, 1H),
23.19, 20.75,







1.78-1.66 (m, 2H),
18.34, 18.17,







1.51-1.40 (m, 2H), 1.35
10.59







(d, J = 6.4 Hz, 3H),








1.38-1.31 (m, 1H),








1.02 (ddt, J = 16.3, 7.7, 2.0 Hz,








1H), 0.80 (t, J = 7.4 Hz,








3H)








7.4 Hz, 3H)



F275
Light
—
—
HRMS-ESI
1H NMR (600 MHz,
19F NMR



Yellow Semi


(m/z)
CDCl3) δ 8.53 (s, 1H),
(CDCl3) δ −111.83



Solid


[M]+
8.34 (d, J = 5.4 Hz,







calcd for
1H), 7.24-7.16 (m,







C27H33FN2O8,
1H), 7.01 (d, J = 5.5 Hz,







532.2221;
1H),







found,
6.88-6.80 (m, 2H), 6.66 (tdd, J = 8.3,







532.2231
2.4, 0.9 Hz, 1H),








5.00 (dq, J = 9.5, 6.4 Hz,








1H), 4.63 (ddd, J = 10.7,








8.4, 7.3 Hz,








1H), 4.38-4.31 (m,








1H), 3.91 (s, 3H),








3.53 (ddd, J = 7.2, 5.3, 1.9 Hz,








1H), 3.45 (dt, J = 9.0,








6.5 Hz, 1H),








3.21 (dt, J = 9.0, 6.5 Hz,








1H), 2.44-2.40 (m,








1H), 2.40 (s, 3H),








2.24-2.12 (m, 1H),








1.79-1.67 (m, 2H),








1.49-1.28 (m, 3H),








1.33 (dd, J = 6.5, 4.6 Hz,








3H), 1.03 (ddt, J = 16.2,








7.7, 2.0 Hz, 1H),








0.77 (t, J = 7.4 Hz,








3H)



F276
White Solid
—
—
ESIMS
—
—






m/z 356








([M + H]+)




F277
White Solid
—
—
ESIMS
—
—






m/z 400








([M + H]+)




F278
White Solid
—
—
ESIMS
—
—






m/z 340








([M + H]+)




F279
White Solid
—
—
ESIMS
—
—






m/z 350








([M + H]+)




F280
White Solid
—
—
HRMS-ESI
1H NMR (600 MHz,
19F NMR






(m/z)
CDCl3) δ 12.05 (d, J = 0.7 Hz,
(CDCl3) δ −111.63






[M]+
1H), 8.47 (d, J = 8.2 Hz,







calcd for
1H), 7.99 (d,







C25H31FN2O7,
J = 5.2 Hz, 1H),







490.2115;
7.25-7.17 (m, 1H),







found,
6.89-6.83 (m, 1H),







490.2124
6.75-6.62 (m, 3H),








4.92 (dq, J = 9.6, 6.3 Hz,








1H), 4.68-4.60 (m,








1H), 4.35 (ddd, J = 7.2,








5.3, 1.8 Hz, 1H),








3.94 (s, 3H),








3.73-3.53 (m, 3H),








2.42-2.33 (m, 1H),








2.18 (dddd, J = 15.8, 10.1,








7.9, 5.3 Hz, 1H),








1.87-1.74 (m, 1H),








1.71-1.61 (m, 1H),








1.56-1.47 (m, 2H), 1.47 (d,








J = 6.4 Hz, 3H),








1.43-1.31 (m, 1H),








1.09 (ddt, J = 16.3, 8.0, 1.8 Hz,








1H), 0.82 (t, J = 7.4 Hz,








3H)



F281
White Solid
—
—
HRMS-ESI
1H NMR (600 MHz,
13C NMR (151 MHz,






(m/z)
CDCl3) δ 12.07 (d, J = 0.7 Hz,
CDCl3)






[M]+
1H), 8.46 (d, J = 8.2 Hz,
δ 171.96,






calcd for
1H), 7.98 (d,
168.69,






C27H36N2O7,
J = 5.2 Hz, 1H),
157.61,






500.2523;
6.86 (d, J = 5.2 Hz, 1H),
155.36,






found,
6.63-6.55 (m, 3H),
148.74,






500.2533
4.91 (dq, J = 9.6, 6.4 Hz,
140.53,







1H), 4.63 (dt, J = 10.7,
139.22,







7.7 Hz, 1H),
130.38,







4.35 (ddd, J = 7.1, 5.2,
123.15,







1.7 Hz, 1H), 3.94 (s,
114.49,







3H), 3.74 (dt, J = 9.0,
109.49, 83.32,







6.5 Hz, 1H),
83.10, 75.57,







3.66-3.55 (m, 2H),
73.09, 56.08,







2.40-2.32 (m, 1H), 2.27 (s,
51.24, 33.26,







6H), 2.23-2.13 (m,
28.13, 23.46,







1H), 1.86-1.77 (m,
21.42, 18.18,







1H), 1.71-1.60 (m,
17.94, 10.63







1H), 1.59-1.47 (m,








2H), 1.47 (d, J = 6.4 Hz, 3H),








1.39-1.29 (m, 1H), 1.01 








(ddt, J = 16.4, 8.2, 1.7 Hz, 1H),








0.85 (t, J = 7.4 Hz,








3H)



F282
White Solid
—
—
HRMS-ESI
1H NMR (600 MHz,
13C NMR (151 MHz,






(m/z)
CDCl3) δ
CDCl3)






[M]+
8.53-8.50 (m, 1H), 8.32 (d, J = 5.4 Hz,
δ 172.45,






calcd for
1H), 6.99 (d, J = 5.5 Hz,
168.89,






C29H38N2O8,
1H),
162.42,






542.2628;
6.62-6.55 (m, 3H),
159.45,






found,
4.88 (dq, J = 9.5, 6.4 Hz,
157.66,






542.2632
1H), 4.64 (ddd, J = 10.7,
146.70,







8.5, 7.4 Hz, 1H),
141.38,







4.33 (ddd, J = 7.2, 5.3,
139.19,







1.8 Hz, 1H), 3.89 (s,
137.51,







3H), 3.74 (dt, J = 9.0,
123.10,







6.5 Hz, 1H),
114.51,







3.64-3.54 (m, 2H), 2.40 (s,
109.82, 83.36,







3H), 2.34 (dt, J = 13.8,
83.22, 75.55,







7.1 Hz, 1H),
72.82, 56.29,







2.27 (s, 6H),
51.29, 33.56,







2.22-2.10 (m, 1H),
28.22, 23.47,







1.82-1.73 (m, 1H),
21.41, 20.75,







1.67-1.57 (m, 1H),
18.22, 17.92,







1.58-1.45 (m, 2H), 1.44 (d,
10.62







J = 6.4 Hz, 3H),








1.32-1.22 (m, 1H),








1.00 (ddt, J = 16.3, 8.1, 1.7 Hz,








1H), 0.85 (t, J = 7.4 Hz,








3H)



F283
White Solid
—
—
HRMS-ESI
1H NMR (600 MHz,
13C NMR (151 MHz,






(m/z)
CDCl3) δ 12.06 (d, J = 0.6 Hz,
CDCl3)






[M]+
1H), 8.49 (d, J = 8.1 Hz,
δ 172.00,






calcd for
1H),
168.69,






C31H36N2O7,
8.03-7.97 (m, 1H),
159.28,






548.2523;
7.59-7.54 (m, 2H),
155.38,






found,
7.54-7.48 (m, 2H),
148.76,






548.2520
7.45-7.38 (m, 2H),
140.78,







7.34-7.28 (m, 1H),
140.54,







7.18-7.11 (m, 2H),
134.42,







6.89-6.84 (m, 1H),
130.38,







5.06 (dq, J = 9.6, 6.4 Hz,
128.70,







1H), 4.64 (dt, J = 10.8,
128.05,







7.7 Hz, 1H),
126.76,







4.48-4.39 (m, 1H),
126.70,







3.94 (s, 3H),
116.74,







3.63-3.54 (m, 1H), 3.47 (dt,
109.50, 83.09,







J = 9.0, 6.6 Hz, 1H),
82.99, 72.83,







3.27 (dt, J = 9.0, 6.5 Hz,
71.44, 56.09,







1H),
51.32, 33.39,







2.47-2.35 (m, 1H), 2.23 
28.13, 23.19,







(dddd, J = 15.8, 10.4, 8.2, 
18.34, 18.15,







5.3 Hz, 1H),
10.58







1.81-1.71 (m, 2H),








1.52-1.42 (m, 3H), 1.40 








(d, J = 6.4 Hz, 3H), 1.08 (ddt,








J = 16.2, 7.9, 2.0 Hz,








1H), 0.79 (t, J = 7.4 Hz,








3H)



F284
White Solid
—
—
HRMS-ESI
1H NMR (CDCl3) δ
19F NMR






(m/z)
8.53 (d, J = 8.3 Hz,
(CDCl3) δ −111.69






[M]+
1H), 8.33 (d, J = 5.4 Hz,







calcd for
1H),







C27H33FN2O8,
7.26-7.14 (m, 1H), 7.00 







532.2221;
(d, J = 5.5 Hz, 1H),







found,
6.75-6.60 (m, 3H),







532.2230
4.90 (dq, J = 9.6, 6.4 Hz,








1H), 4.64 (ddd, J = 10.7,








8.4, 7.3 Hz, 1H),








4.34 (ddd, J = 7.2, 5.3,








1.8 Hz, 1H), 3.90 (s,








3H), 3.73-3.50 (m,








3H), 2.40 (s, 3H),








2.39-2.30 (m, 1H),








2.20-2.08 (m, 1H),








1.85-1.71 (m, 1H),








1.69-1.56 (m, 1H),








1.54-1.45 (m, 2H), 1.44 (d,








J = 6.4 Hz, 3H),








1.37-1.22 (m, 1H),








1.07 (ddt, J = 16.3, 7.9, 2.0 Hz,








1H), 0.82 (t, J = 7.4 Hz,








3H)



F285
White Solid
—
—
HRMS-ESI
1H NMR (600 MHz,
13C NMR (151 MHz,






(m/z)
CDCl3) δ 8.53 (s, 1H),
CDCl3)






[M]+
8.33 (d, J = 5.5 Hz,
δ 172.43,






calcd for
1H), 7.39-7.31 (m,
168.89,






C27H33BrN2O8,
2H), 7.00 (d, J = 5.4 Hz,
162.41,






592.1427;
1H),
159.46,






found,
6.99-6.96 (m, 2H), 4.99 
158.91,






592.1420
(dq, J = 9.5, 6.4 Hz, 1H),
146.69,







4.62 (ddd, J = 10.7, 8.3, 
141.35,







7.3 Hz, 1H),
137.53,







4.35-4.27 (m, 1H), 3.90 (s, 3H),
132.16,







3.53 (ddd, J = 7.3, 5.3,
118.29,







1.8 Hz, 1H), 3.44 (dt,
113.46,







J = 9.0, 6.6 Hz, 1H),
109.85, 83.40,







3.20 (dt, J = 9.1, 6.5 Hz,
82.94, 72.29,







1H), 2.39 (s, 3H),
71.27, 56.30,







2.43-2.31 (m, 1H),
51.33, 33.60,







2.23-2.09 (m, 1H),
28.04, 23.14,







1.71 (qdt, J = 12.6,
20.75, 18.31,







5.6, 3.2 Hz, 2H),
18.04, 10.56







1.48-1.33 (m, 3H),








1.32 (d, J = 6.3 Hz, 3H),








1.03 (ddt, J = 16.2,








7.4, 2.0 Hz, 1H),








0.77 (t, J = 7.4 Hz, 3H)



F286
White Solid
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR






(m/z)
8.53 (d, J = 8.5 Hz,
(CDCl3) δ






[M]+
1H), 8.38-8.30 (m,
172.45,






calcd for
1H), 7.18 (t, J = 8.1 Hz,
168.90,






C27H33ClN2O8,
1H), 7.13 (t, J = 2.2 Hz,
162.41,






548.1925;
1H), 7.01 (d, J = 5.5 Hz,
160.42,






found,
1H),
159.46,






548.1924
6.95 (dddd, J = 9.8, 7.9,
146.70,







2.2, 0.9 Hz, 2H),
141.37,







5.00 (dq, J = 9.7, 6.4 Hz,
137.53,







1H), 4.70-4.57 (m,
134.66,







1H), 4.35 (dd, J = 9.7,
130.07,







7.2 Hz, 1H), 3.91 (s,
121.53,







3H), 3.59-3.50 (m,
117.09,







1H), 3.50-3.40 (m,
114.72,







1H), 3.20 (dt, J = 8.9,
109.83, 83.34,







6.5 Hz, 1H),
82.97, 72.23,







2.45-2.30 (m, 1H), 2.40 (s,
71.24, 56.30,







3H), 2.26-2.11 (m
51.34, 33.61,







1H), 1.81-1.65 (m,
28.01, 23.14,







2H), 1.53-1.36 (m,
20.75, 18.32,







3H), 1.35-1.28 (m,
18.05, 10.55







3H), 1.09-0.96 (m,








1H), 0.78 (t, J = 7.4 Hz,








3H)



F287
White Solid
—
—
ESIMS
1H NMR (CDCl3) δ
13C NMR






m/z 590
8.58-8.45 (m, 1H),
(CDCl3) δ






([M − H]−)
8.34 (dd, J = 5.5, 1.4 Hz,
172.51,







7.60-7.48 1H),
168.91,







(m, 4H), 7.41 (td, J = 8.6,
162.42,







8.0, 2.0 Hz, 2H),
159.46,







7.30 (tt, J = 6.8, 1.4 Hz,
159.32,







1H),
146.71,







7.19-7.11 (m, 2H),
141.40,







7.04-6.96 (m, 1H), 5.03 
140.80,







(dq, J = 10.1, 6.4 Hz, 1H),
137.53,







4.64 (dt, J = 11.1, 7.8 Hz,
134.37,







1H), 4.43 (dd, J = 9.7,
128.70,







7.1 Hz, 1H),
128.03,







3.90 (d, J = 1.4 Hz, 3H),
126.76,







3.64-3.51 (m, 1H),
126.68,







3.46 (dt, J = 9.5, 6.6 Hz,
116.76,







1H), 3.26 (dt, J = 9.4,
109.83, 83.16,







6.6 Hz, 1H),
83.07, 72.56,







2.40 (s, 3H),
71.41, 56.30,







2.43-2.31 (m, 1H),
51.38, 33.67,







2.25-2.13 (m, 2H),
28.21, 23.18,







1.84-1.67 (m, 2H),
20.76, 18.38,







1.48-1.40 (m, 2H), 1.37 
18.13, 10.57







(d, J = 6.0 Hz, 3H),








1.12-1.00 (m, 1H), 0.78 (t,








J = 7.3 Hz, 3H)



F288
White Solid
—
—
ESIMS
1H NMR (CDCl3) δ
13C NMR






m/z 513.5
12.06 (d, J = 0.7 Hz,
(CDCl3) δ






([M + H]+)
1H), 8.48 (d, J = 8.1 Hz,
171.99,







1H), 8.00 (d, J = 5.2 Hz,
168.68,







1H),
159.21,







7.44-7.31 (m, 2H),
155.38,







7.07-7.00 (m, 2H),
148.75,







6.93-6.83 (m, 1H),
142.53,







5.30 (dd, J = 1.6, 0.8 Hz,
140.54,







1H), 5.09-4.97 (m,
134.37,







2H), 4.62 (dt, J = 10.8,
130.37,







7.6 Hz, 1H),
126.49,







4.48-4.34 (m, 1H),
116.08,







3.94 (s, 3H),
110.81,







3.57 (ddd, J = 7.1, 5.3, 1.8 Hz,
109.50, 83.03,







1H), 3.45 (dt, J = 9.1,
82.91, 72.83,







6.6 Hz, 1H),
71.43, 56.09,







3.26 (dt, J = 9.1, 6.5 Hz,
51.31, 33.38,







1H), 2.42 (ddd, J = 14.8,
28.12, 23.18,







7.2, 5.3 Hz, 1H),
21.90, 18.32,







2.29-2.15 (m, 1H)
18.11, 10.57







2.15-2.11 (m, 3H),








1.87-1.71 (m, 2H),








1.52-1.41 (m, 3H),








1.36 (d, J = 6.4 Hz,








3H), 1.11-1.00 (m,








1H), 0.78 (t, J = 7.4 Hz, 3H)



F289
White Solid
—
—
ESIMS
1H NMR (CDCl3) δ
13C NMR (151 MHz,






m/z 555.6
8.54 (d, J = 7.9 Hz,
CDCl3)






([M + H]+)
1H), 8.34 (d, J = 5.4 Hz,
δ 172.49,







1H),
168.90,







7.53-7.31 (m, 2H),
162.41,







7.13-6.93 (m, 3H) 5.30 (dd, J = 1.6,
159.46,







0.9 Hz, 1H),
159.25,







5.19-4.94 (m, 2H),
146.70,







4.78-4.57 (m, 1H),
142.55,







4.48-4.19 (m, 1H), 3.90 (s,
141.39,







3H), 3.65-3.37 (m,
134.32,







2H), 3.30-3.17 (m,
129.33,







1H), 2.40 (s, 3H),
126.48,







2.45-2.31 (m, 1H),
116.49,







2.23-2.14 (m, 1H),
116.09,







2.14-2.05 (m, 3H),
110.77,







1.71 (ddd, J = 17.7, 
109.83, 83.09,







9.4, 4.1 Hz, 2H),
82.98, 72.57,







1.53-1.30 (m, 3H), 1.34 
71.41, 56.29,







(d, J = 6.4 Hz, 3H),
51.37, 33.66,







1.04 (ddd, J = 16.3, 
28.21, 23.17,







5.9, 3.8 Hz, 1H),
20.75, 18.36,







0.88-0.64 (m, 3H)
18.08, 10.56


F290
White Solid
—
—
ESIMS
1H NMR (CDCl3) δ
13C NMR






m/z 545.5
12.02 (d, J = 0.6 Hz,
(CDCl3) δ






([M + H]+)
1H), 8.50 (d, J = 8.1 Hz,
171.75,







1H), 7.99 (d, J = 5.2 Hz,
168.73,







1H), 6.87 (dd,
159.07,







J = 5.3, 0.6 Hz, 1H),
155.37,







6.65-6.60 (m, 3H),
154.41,







5.12 (dq, J = 9.5, 6.4 Hz,
148.74,







1H), 5.00 (ddd, J = 7.7,
140.59,







5.5, 2.1 Hz,
139.27,







1H), 4.66 (ddd, J = 10.8,
130.29,







8.2, 7.2 Hz, 1H),
123.68,







4.50 (dd, J = 9.5, 7.7 Hz,
114.01,







1H),
109.54, 80.79,







4.01-3.92 (m, 2H), 3.94 (s, 3H),
80.60, 72.57,







2.43 (dtd, J = 13.7,
69.61, 56.09,







7.1, 6.7, 2.0 Hz, 1H),
51.22, 33.18,







2.28 (s, 6H),
29.42, 21.89,







2.26-2.18 (m, 1H),
21.40, 18.37,







1.93-1.75 (m, 2H),
18.04, 10.03







1.63-1.43 (m, 3H), 1.41 (d,








J = 6.4 Hz, 3H),








1.30 (td, J = 6.8, 6.3, 3.4 Hz,








1H), 0.84 (t, J = 7.4 Hz,








3H)



F291
Colorless
—
—
HRMS-ESI
1H NMR (CDCl3) δ
13C NMR



Semi Solid


(m/z)
8.56 (d, J = 8.4 Hz,
(CDCl3) δ






[M]+
1H), 8.34 (d, J = 5.4 Hz,
172.23,






calcd for
1H), 7.01 (d, J = 5.5 Hz,
168.89,






C30H38N2O10,
1H),
162.45,






586.2532;
6.65-6.59 (m, 3H),
159.45,






found,
5.16-5.06 (m, 1H),
159.09,






586.2526
5.06-4.94 (m, 1H),
154.42,







4.66 (ddd, J = 10.7, 
146.72,







8.3, 7.1 Hz, 1H),
141.28,







4.53-4.43 (m, 1H), 3.95 
139.25,







(tdt, J = 4.9, 2.5, 1.0 Hz, 3H),
137.52,







3.91 (s, 3H),
123.64,







2.47-2.34 (m, 1H), 2.40 (s,
114.03,







3H), 2.28 (d, J = 0.8 Hz,
109.86, 80.86,







6H),
80.70, 72.31,







2.24-2.15 (m, 1H),
69.59, 56.30,







1.83-1.75 (m, 1H),
51.28, 33.46,







1.59-1.50 (m, 2H), 1.39 
29.51, 21.88,







(d, J = 6.4 Hz, 3H),
21.40, 20.75,







1.31-1.21 (m, 2H), 0.83 (t,
18.41, 18.02,







J = 7.4 Hz, 3H)
10.03


F292
White Solid
—
—
ESIMS
—
—






m/z 398








([M + H]+)




F293
White Solid
—
—
ESIMS
—
—






m/z 394








([M + H]+)




F294
White Solid
—
—
ESIMS
—
—






m/z 362








([M + H]+)





*Cmpd. No. - Compound Number


*Phys. App. - Physical Appearance


*MP - Melting Point; ° C.


*IR - Infrared Spectroscopy; Thin Film; cm−1


*1H NMR were run at 400 MHz unless specified otherwise.


*13C NMR were run at 101 MHz unless specified otherwise.


*19F NMR were run at 376 MHz unless specified otherwise.













TABLE 3







Rating Scale for 


Results of Biological Evaluation










Biology Rating Table




(% Control)
Rating







80-100
A



More than 0-Less than 80
B



Not Tested
C



≦0
D

















TABLE 4







Biological Activity - Disease Control 


in High Volume Applications (100 ppm)











Compound
PUCCRT
SEPTTR













Number
1DP
3DC
1DP
3DC







F1
C
C
C
C



F2
C
C
C
C



F3
C
C
C
C



F4
C
C
C
C



F5
C
C
C
C



F6
C
C
C
C



F7
C
C
C
C



F8
C
C
C
C



F9
C
C
C
C



F10
C
C
C
C



F11
C
C
C
C



F12
C
C
C
C



F13
C
C
C
C



F14
A
A
D
A



F15
A
A
A
A



F16
A
A
A
A



F17
A
A
A
A



F18
A
A
A
A



F19
A
A
A
A



F20
A
A
A
A



F21
A
A
B
B



F22
A
A
A
A



F23
A
A
A
A



F24
A
A
A
A



F25
A
A
A
A



F26
A
A
A
A



F27
A
A
A
A



F28
A
A
A
A



F29
A
A
A
A



F30
A
A
A
B



F31
A
A
A
A



F32
A
A
A
A



F33
A
A
B
A



F34
A
A
A
A



F35
A
A
A
A



F36
A
A
A
A



F37
A
A
A
A



F38
A
A
A
A



F39
A
A
A
A



F40
A
A
B
B



F41
A
A
B
A



F42
A
A
A
A



F43
A
A
A
A



F44
A
A
A
A



F45
A
A
A
A



F46
A
A
A
A



F47
A
A
A
A



F48
A
A
A
A



F49
A
A
A
A



F50
A
A
A
B



F51
A
A
A
A



F52
A
A
A
A



F53
A
A
A
B



F54
A
A
A
B



F55
A
A
A
A



F56
A
A
A
A



F57
A
A
A
A



F58
A
A
A
A



F59
A
A
A
A



F60
A
A
A
A



F61
A
A
A
A



F62
A
A
A
A



F63
A
A
A
A



F64
B
D
B
B



F65
A
A
A
B



F66
A
A
A
B



F67
A
A
A
B



F68
A
A
A
A



F69
A
A
A
A



F70
B
B
B
B



F71
B
A
B
B



F72
A
A
A
A



F73
A
A
B
A



F74
A
A
A
A



F75
A
A
A
A



F76
A
A
A
A



F77
A
A
A
A



F78
A
A
A
A



F79
A
A
A
A



F80
A
A
A
A



F81
A
A
A
A



F82
B
B
D
B



F83
A
A
A
A



F84
B
B
B
B



F85
D
B
D
B



F86
A
A
A
A



F87
A
A
A
A



F88
A
A
A
A



F89
A
A
A
A



F90
A
A
A
A



F91
A
A
A
A



F92
A
A
A
A



F93
A
A
A
A



F94
B
D
B
B



F95
A
A
A
A



F96
A
A
A
A



F97
A
A
A
A



F98
A
A
A
A



F99
A
A
A
A



F100
A
A
A
A



F101
A
A
A
A



F102
A
A
A
A



F103
A
A
A
A



F104
A
D
A
D



F105
A
D
A
B



F106
A
A
A
A



F107
A
A
A
A



F108
A
A
A
A



F109
A
A
A
A



F110
A
A
A
A



F111
A
D
B
B



F112
A
A
A
A



F113
B
B
D
B



F114
A
A
A
A



F115
A
B
A
B



F116
A
A
A
A



F117
A
A
D
A



F118
A
A
A
B



F119
A
A
A
A



F120
A
A
A
A



F121
A
A
A
A



F122
A
A
A
A



F123
A
A
A
A



F124
A
A
A
A



F125
A
A
A
A



F126
A
A
A
A



F127
A
A
A
A



F128
A
B
A
D



F129
A
A
A
D



F130
A
A
A
A



F131
A
A
A
A



F132
A
A
A
A



F133
A
A
A
A



F134
A
A
A
A



F135
A
A
A
A



F136
A
A
A
A



F137
A
A
A
A



F138
A
A
A
A



F139
A
A
A
A



F140
A
A
A
A



F141
A
A
A
A



F142
A
A
B
A



F143
A
A
A
B



F144
A
A
A
A



F145
A
A
A
A



F146
A
A
A
A



F147
A
A
A
A



F148
A
A
A
A



F149
A
A
A
B



F150
A
A
A
A



F151
A
A
A
A



F152
A
A
A
A



F153
A
A
A
A



F154
A
A
A
A



F155
A
A
A
A



F156
A
A
A
A



F157
A
A
A
A



F158
A
A
A
A



F159
A
A
A
A



F160
A
A
A
A



F161
A
A
A
A



F162
A
B
A
A



F163
A
A
A
B



F164
A
A
A
A



F165
A
A
A
A



F166
A
A
A
A



F167
A
A
A
A



F168
A
A
A
A



F169
A
A
A
A



F170
A
A
A
A



F171
A
A
A
A



F172
A
A
A
A



F173
A
A
A
A



F174
C
C
C
C



F175
C
C
C
C



F176
C
C
C
C



F177
C
C
C
C



F178
C
C
C
C



F179
C
C
C
C



F180
C
C
C
C



F181
C
C
C
C



F182
C
C
C
C



F183
C
C
C
C



F184
C
C
C
C



F185
C
C
C
C



F186
C
C
C
C



F187
C
C
C
C



F188
C
C
C
C



F189
C
C
C
C



F190
C
C
C
C



F191
C
C
C
C



F192
C
C
C
C



F193
C
C
C
C



F194
C
C
C
C



F195
C
C
C
C



F196
C
C
C
C



F197
C
C
C
C



F198
C
C
C
C



F199
C
C
C
C



F200
C
C
C
C



F201
C
C
C
C



F202
C
C
C
C



F203
C
C
C
C



F204
C
C
C
C



F205
C
C
C
C



F206
C
C
C
C



F207
C
C
C
C



F208
C
C
C
C



F209
C
C
C
C



F210
A
A
A
A



F211
A
A
A
A



F212
A
A
B
B



F213
A
A
B
B



F214
A
A
A
A



F215
A
A
A
A



F216
A
A
A
A



F217
A
A
A
A



F218
A
A
A
B



F219
A
A
A
B



F220
A
A
A
A



F221
A
B
A
B



F222
A
A
A
A



F223
A
A
A
A



F224
A
B
B
B



F225
A
A
A
A



F226
C
C
C
C



F227
C
C
C
C



F228
C
C
C
C



F229
C
C
C
C



F230
C
C
C
C







PUCCRT - Wheat brown rust (Puccinia triticina)



SEPTTR - Wheat leaf blotch (Septoria tritici)



1DP - 1 Day Protectant



3DC - 3 Day Curative













TABLE 5







Biological Activity - Disease Control in High Volume 


(100 ppm) and Low Volume Applications (121.5 g/H)










PUCCRT*
SEPTTR*












1 DP*
3 DC*
1 DP*
3 DC*










Rate
Rate















Compound
121.5 
100
121.5 
100
121.5 
100
121.5 
100


Number
g/H*
ppm*
g/H*
ppm*
g/H*
ppm*
g/H*
ppm*





F231
C
C
C
C
C
C
C
C


 


F232
C
A
C
A
C
A
C
B


 


F233
A
A
B
A
A
A
A
A


 


F234
A
A
D
A
A
A
D
A


 


F235
A
A
B
A
A
A
B
A


 


F236
B
A
D
B
A
B
B
B


 


F237
A
A
B
A
D
B
B
B


 


F238
C
C
C
C
C
C
C
C


 


F239
C
B
C
D
C
D
C
B


 


F240
A
A
A
A
A
A
A
A


 


F241
A
A
A
A
D
A
D
A


 


F242
A
A
B
A
B
A
B
A


 


F243
A
A
A
A
B
A
A
A


 


F244
C
C
C
C
C
C
C
C


 


F245
C
A
C
B
C
B
C
A


 


F246
C
C
C
C
C
C
C
C


 


F247
C
A
C
A
C
A
C
B


 


F248
C
C
C
C
C
C
C
C


 


F249
C
A
C
A
C
B
C
B


 


F250
B
C
A
C
D
C
B
C


 


F251
A
C
A
C
D
C
D
C


 


F252
A
C
A
C
B
C
B
C


 


F253
A
C
A
C
D
C
D
C


 


F254
A
C
A
C
D
C
D
C


 


F255
A
C
A
C
B
C
B
C


 


F256
B
C
A
C
D
C
B
C


 


F257
A
C
A
C
A
C
A
C


 


F258
A
C
A
C
B
C
B
C


 


F259
A
C
A
C
D
C
A
C


 


F260
A
C
A
C
B
C
A
C


 


F261
C
C
C
C
C
C
C
C


 


F262
C
B
C
A
C
A
C
A


 


F263
C
C
C
C
C
C
C
C


 


F264
C
B
C
A
C
A
C
B


 


F265
A
A
B
A
A
A
C
A


 


F266
A
C
A
C
A
C
C
C


 


F267
C
A
C
A
C
A
C
A


 


F268
C
C
C
C
C
C
C
C


 


F269
C
C
C
C
C
C
C
C


 


F270
C
A
C
A
C
A
C
B


 


F271
C
A
C
A
C
A
C
A


 


F272
C
A
C
A
C
A
C
A


 


F273
C
A
C
A
C
A
C
B


 


F274
A
A
B
A
A
A
A
A


 


F275
A
A
A
A
A
A
A
A


 


F276
C
C
C
C
C
C
C
C


 


F277
C
C
C
C
C
C
C
C


 


F278
C
C
C
C
C
C
C
C


 


F279
C
C
C
C
C
C
C
C


 


F280
C
A
C
B
C
A
C
A


 


F281
C
A
C
B
C
B
C
B


 


F282
A
A
A
A
A
A
A
A


 


F283
C
A
C
B
C
A
C
B


 


F284
A
A
A
A
A
A
A
A


 


F285
A
A
A
B
A
A
A
A


 


F286
A
A
B
A
A
A
A
A


 


F287
A
A
A
A
A
A
A
A


 


F288
C
A
C
A
C
A
C
A


 


F289
A
A
A
A
A
A
A
A


 


F290
C
A
C
A
C
B
C
B


 


F291
C
A
C
B
C
A
C
A


 


F292
C
C
C
C
C
C
C
C


 


F293
C
C
C
C
C
C
C
C


 


F294
C
C
C
C
C
C
C
C





*PUCCRT - Wheat Brown Rust (Puccinia triticina)


*SEPTTR - Wheat Leaf Blotch (Septoria tritici)


*1 DP - 1 Day Protectant


*3 DC - 3 Day Curative


*g/H - Grams Per Hectare


*ppm - Parts Per Million













TABLE 6







Biological Activity - Disease Control


in High Volume Applications (100 ppm)














ALTESO*
CERCBE*
COLLLA*
ERYSCI*
ERYSGH*
ERYSGT*








Cmpd. No.
1 DP*
















F20
B
A
A
B
B
B


 


F26
C
A
A
B
C
B


 


F28
B
A
A
B
A
B


 


F29
A
A
A
A
A
A


 


F30
B
B
A
B
B
D


 


F31
B
A
A
D
B
B


 


F34
B
A
A
B
B
B


 


F35
A
A
A
A
A
B


 


F36
A
A
A
B
B
D


 


F37
A
A
A
A
A
B


 


F38
A
A
A
A
A
B


 


F39
A
A
A
A
A
A


 


F78
C
C
A
C
C
C


 


F130
A
A
C
A
B
C


 


F132
A
B
C
B
B
C


 


F134
B
A
C
B
B
C


 


F138
A
A
A
B
B
C


 


F139
A
A
A
B
D
C


 


F140
A
A
A
D
B
C


 


F141
A
A
A
B
A
C


 


F154
A
A
A
A
A
C


 


F155
A
A
A
A
A
C


 


F165
A
A
C
B
B
C


 


F166
A
A
C
A
A
C


 


F169
A
A
C
A
B
C


 


F170
A
A
C
B
B
C


 


F171
A
A
C
A
B
C


 


F172
A
A
C
A
B
C


 


F173
A
A
C
B
B
C


 


F217
C
C
A
C
C
C


 


F237
B
A
B
D
B
C


 


F241
B
A
A
D
B
C


 


F242
D
A
A
D
B
C


 


F250
B
B
B
D
B
C


 


F251
B
B
A
D
D
C


 


F252
B
B
A
D
B
C


 


F253
B
D
A
D
B
C


 


F254
B
B
A
D
B
C


 


F255
B
B
A
D
B
C





ALTESO - Tomato Early Blight (Alternaria solani)


*CERCBE - Leaf Spot of Sugar Beets (Cercospora beticola)


*COLLLA - Cucumber Anthracnose (Glomerella lagenarium; Anamorph: Colletotricum lagenarium)


*ERYSCI - Powdery Mildew of Cucumber (Erysiphe cichoracearum)


*ERYSGH - Barley Powdery Mildew (Blumeria graminis f.sp. hordei; Synonym: Erysiphe graminis f.sp. hordei)


*ERYSGT - Wheat Powdery Mildew (Blumeria graminis f.sp. tritici; Synonym: Erysiphe graminis f.sp. tritici)


*1 DP - 1 Day Protectant













TABLE 7







Biological Activity - Disease Control 


in High Volume Applications (100 ppm)












Cmpd.
LEPTNO*
PYRIOR*
RHYNSE*
UNCINE*
VENTIN*








No.
1 DP*















F20
A
A
A
B
B


 


F26
A
C
C
B
C


 


F28
B
A
A
B
A


 


F29
A
A
C
A
A


 


F30
A
A
C
B
A


 


F31
A
A
C
B
C


 


F34
C
A
C
B
C


 


F35
C
A
C
A
C


 


F36
C
A
C
B
C


 


F37
C
A
C
A
C


 


F38
C
A
C
A
C


 


F39
A
A
A
B
A


 


F78
C
C
C
C
C


 


F130
C
A
A
B
C


 


F132
C
B
B
B
C


 


F134
C
A
A
B
C


 


F138
C
A
A
B
C


 


F139
C
A
A
B
C


 


F140
C
A
A
B
C


 


F141
A
A
A
B
B


 


F154
C
A
A
B
C


 


F155
C
A
B
B
C


 


F165
C
A
A
B
C


 


F166
C
A
A
B
C


 


F169
C
A
A
B
C


 


F170
C
A
A
B
C


 


F171
C
A
A
B
C


 


F172
C
A
A
B
C


 


F173
C
A
A
B
C


 


F217
C
C
C
C
C


 


F237
C
A
D
B
A


 


F241
C
A
B
B
B


 


F242
C
A
D
B
B


 


F250
A
A
B
B
A


 


F251
A
A
B
B
D


 


F252
A
A
A
B
B


 


F253
A
A
B
B
A


 


F254
A
A
A
B
A


 


F255
A
A
A
A
A





*LEPTNO - Wheat Glume Blotch (Leptosphaeria nodorum)


*PYRIOR - Rice Blast (Magnaporthe grisea; Anamorph: Pyricularia oryzae)


*RHYNSE - Barley Scald (Rhyncosporium secalis)


*UNCINE - Grape Powdery Mildew (Uncinula necator)


*VENTIN - Apple Scab (Venturia inaequalis)


*1 DP - 1 Day Protectant













TABLE 8







Biological Activity - Disease Control 


in High Volume Applications (25 ppm)










Compound
PHAKPA*











Number
1DP*
3DC*







F20
A
A



F26
A
A



F28
A
B



F29
A
C



F30
A
B



F34
A
A



F35
A
C



F36
A
A



F37
A
C



F38
A
A



F39
A
A



F44
A
C



F45
A
A



F46
A
C



F47
D
C



F59
A
C



F68
A
C



F76
A
C



F77
A
C



F78
A
A



F79
A
C



F80
A
A



F81
A
C



F95
A
A



F130
A
B



F133
A
B



F138
A
A



F139
A
A



F140
A
A



F141
A
A



F154
A
A



F155
A
A



F165
A
B



F166
A
A



F170
A
B



F172
A
A



F217
A
C



F237
A
D



F241
A
B



F242
A
B



F243
A
B



F250
B
D



F251
A
B



F252
A
B



F253
B
D



F254
A
B



F255
A
B







*PHAKPA - Asian Soybean Rust (Phakopsora pachyrhizi)



*1DP - 1 Day Protectant



*3DC - 3 Day Curative

## Claims

1. A compound of Formula I:



wherein:
X is H;
Y is Q;
Q is




R1 is H, alkyl, alkenyl, aryl, —C(O)R4, each substituted with 0, 1 or multiple R4;
R2 is alkyl, alkenyl, aryl —C(O)R4, each substituted with 0, 1 or multiple R4;
R3 is H, —C(O)R6 or —CH2OC(O)R6;
R4 is alkyl, alkenyl, halo, haloalkyl, alkoxy, or aryl;
R5 is alkyl, alkoxy, benzyl, benzyloxy, each substituted with 0, 1, or multiple R7, wherein each R7 may be substituted with 0, 1, or multiple R4;
R6 is alkyl or alkoxy, each substituted with 0, 1, or multiple R4; and
R7 is alkyl, alkenyl, halo, haloalkyl, alkoxy, aryl, —Si(R4)3, —C(O)R4, —S(O)nR4, each substituted with 0, 1, or multiple R4.

2. The compound according to claim 1 wherein R1 is chosen from H, alkyl, alkenyl, aryl, or —C(O)R4, each substituted with 0, 1, or multiple R4, and
wherein R2 is chosen from alkyl, alkenyl, aryl, or —C(O)R4, each substituted with 0, 1, or multiple R4.

3. The compound according to claim 1 wherein R1 and R2 are independently alkyl, alkenyl, aryl, or —C(O)R4, each substituted with 0, 1, or multiple R4.

4. A method for the treatment of plant disease, comprising the steps of:
applying a fungicidally effective amount of at least one of the compounds of claim 1 to at least one surface selected from the group consisting of: at least one surface of a plant, an area adjacent to a plant, soil in contact with a plant, soil adjacent to a plant, seeds, and equipment for use in agriculture.

5. The method of claim 4, wherein the fungicidally effective amount of the compound of Formula I is applied to a surface in the range of about 0.01 g/m2 to about 0.45 g/m2 of the compound of Formula I.

6. The compound of claim 1, wherein the compound is:

7. A method for the treatment of plant disease, comprising the steps of:
applying a fungicidally effective amount the compound of claim 6 to at least one surface selected from the group consisting of: at least one surface of a plant, an area adjacent to a plant, soil in contact with a plant, soil adjacent to a plant, seeds, and equipment for use in agriculture.

8. The method of claim 7, wherein the fungicidally effective amount of the compound of Formula I is applied to a surface in the range of about 0.01 g/m2 to about 0.45 g/m2 of the compound of Formula I.

9. A compound of Formula I:



wherein:
X is H;
Y is Q;
Q is




R1 is alkyl, alkenyl, aryl, —C(O)R4, each substituted with 0, 1 or multiple R4;
R2 is H, alkyl, alkenyl, aryl —C(O)R4, each substituted with 0, 1 or multiple R4;
R3 is H, —C(O)R6 or —CH2OC(O)R6;
R4 is alkyl, alkenyl, halo, haloalkyl, alkoxy, or aryl;
R5 is alkyl, alkoxy, benzyl, benzyloxy, each substituted with 0, 1, or multiple R7, wherein each R7 may be substituted with 0, 1, or multiple R4;
R6 is alkyl or alkoxy, each substituted with 0, 1, or multiple R4; and
R7 is alkyl, alkenyl, halo, haloalkyl, alkoxy, aryl, —Si(R4)3, —C(O)R4, —S(O)nR4, each substituted with 0, 1, or multiple R4.

10. The compound according to claim 9 wherein R1 is chosen from alkyl, alkenyl, aryl, or —C(O)R4, each substituted with 0, 1, or multiple R4, and wherein R2 is chosen from H, alkyl, alkenyl, aryl, or —C(O)R4, each substituted with 0, 1, or multiple R4.

11. A method for the treatment of plant disease, comprising the steps of:
applying a fungicidally effective amount of at least one of the compounds of claim 9 to at least one surface selected from the group consisting of: at least one surface of a plant, an area adjacent to a plant, soil in contact with a plant, soil adjacent to a plant, seeds, and equipment for use in agriculture.

12. The method of claim 11, wherein the fungicidally effective amount of the compound of Formula I is applied to a surface in the range of about 0.01 g/m2 to about 0.45 g/m2 of the compound of Formula I.