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DOI:10.15227/orgsyn.070.0035

Organic Syntheses, Coll. Vol. 9, p.610 (1998); Vol. 70, p.35 (1992).

(R)-(−)-10-METHYL-1(9)-OCTAL-2-ONE[2(3H)-Naphthalenone, 4,4a,5,6,7,8-hexahydro-4a-methyl-, (R)-]

Submitted by G. Revial and M. Pfau1.
Checked by Graham N. Maw and Robert K. Boeckman, Jr..

1. Procedure
A. Imines (1). In a 1000-mL, round-bottomed flask, fitted with a toluene-filled Dean-Stark water
separator, 100.0 g (0.825 mol) of (S)-(−)-α-methylbenzylamine (Note 1), 92.5 g (0.825 mol) of 2methylcyclohexanone (Note 2) and 100 mL of toluene are heated at reflux temperature under a nitrogen
atmosphere. After 24 hr, ca. 15 mL of water (ca. 100% theor.) has been removed azeotropically.
B. (R)-(+)-2-Methyl-2-(3-oxobutyl)cyclohexanone (2). The solution of imines 1 is cooled in an ice
bath and 72.5 mL (61.0 g, 0.870 mol, ca. 1.05 equiv) of freshly distilled methyl vinyl ketone (Note 3) is
added with a syringe, with magnetic stirring, under a nitrogen atmosphere. The flask is then heated at
ca. 40°C for 24 hr.
The slightly yellow solution is cooled in an ice bath and 60 mL of glacial acetic acid (ca. 1 mol) and50 mL of water are added. Hydrolysis is achieved by stirring the heterogeneous mixture at room
temperature for 2 hr. The now clear solution is poured into a 2000-mL separatory funnel containing 100
mL of brine and 160 mL of water and is extracted five times with a 50:50 mixture of ether-petroleum
ether (35–60°C) (1000-mL total amount). The organic phase is washed efficiently with 20 mL of 10%hydrochloric acid, 20 mL of water, and two 10-mL portions of brine.
The aqueous layer is kept for recovery of the amine (see D below).
The pale yellow organic layer is dried over a small amount of anhydrous magnesium sulfate andfiltered. The solvents are removed with a rotary evaporator at ca. 40°C and the crude diketone 2 (ca. 145g) is used directly for the next step.
C. (R)-(−)-10-Methyl-1(9)-octal-2-one (3). Dry methanol (600 mL) is added to the crude diketone 2

contained in a 2000-mL, round-bottomed flask and a rubber septum is fitted. The solution is stirred
at room temperature for 15 min under a slight stream of nitrogen to remove traces of oxygen. A 25 wt.
% solution of sodium methoxide in methanol (Note 4) is then introduced dropwise with a syringe, understirring, until a slightly red color develops (Note 5). At this point, 15 mL (ca. 0.07 mol) of the sodium
methoxide solution is added and the mixture is heated at 60°C for 10 hr under a nitrogen atmosphere.
The solution is cooled and the now deep red solution is neutralized with glacial acetic acid (ca. 4.5 mL)
until the color turns yellow. Methanol is removed with a rotary evaporator until a thick paste (sodium
acetate) results; this is dissolved with 200 mL of water. Extraction is effected in a 2000-mL separatory
funnel using four portions of a 50:50 mixture (1000 mL total amount) of ether-petroleum ether (35–60°
C). The pale orange organic phase is washed twice with 40 mL of water, then twice with 20 mL ofbrine. The organic layer is dried over a small amount of anhydrous magnesium sulfate and filtered. The
solvents are removed with a rotary evaporator at ca. 40°C and the red oily residue of crude octalone 3 isdistilled under reduced pressure to afford ca. 110 g of a colorless oil, bp 70°C (2 mm) (Note 6). The oil
is purified by recrystallization at a low temperature with an apparatus designed for this purpose.2 The oil
is dissolved with stirring in a 1000-mL, round-bottomed flask with 370 mL of pentane under a nitrogen
atmosphere. The flask is then cautiously cooled in a Dewar flask containing liquid nitrogen until thesolution is solid. The Dewar flask is removed and the temperature is allowed to rise, while magnetic
stirring is resumed. When a crystalline mass in suspension appears suddenly (Note 7), an acetone bathadjusted to about −10°C is installed. When only a few crystals remain in suspension, the bathtemperature is slowly lowered to −35°C, inducing crystallization. After the mixture has been kept at−35°C for 15 min, magnetic stirring is stopped and efficient filtration is performed through the filter
stick. Still at −35°C, the compound is washed with 40 mL of pentane. The solution is stirred vigorously
for 5 min and filtered as before. The washing operation is repeated two more times. The flask is warmed
to room temperature and the oil is distilled as before, bp 70°C (2 mm), to afford 60–65 g (44–48%
overall yield from 2-methylcyclohexanone) of methyloctalone 3 [>99% chemical purity, capillary GLC(Note 6)], [α]D20 −210° (ethanol, c 1.00), optical purity 96% (Note 8).
D. Recovery of (S)-(−)-α-methylbenzylamine. The aqueous layer (see above, B, 3rd paragraph)contained in a 1000-mL flask is cooled in an ice bath under a nitrogen atmosphere. An aqueous 10%
sodium hydroxide solution is added with stirring until a pH of 12–14 (Note 9) is reached. The mixture istransferred to a 2000-mL separatory funnel and extracted three times with ether (1000-mL total
amount). The organic phase is washed twice with 100 mL of water and twice with 30 mL of brine, thendried over potassium carbonate and filtered. The solution is concentrated at room temperature with arotary evaporator and distilled under reduced pressure to afford 85–90 g (85–90% yield) of the amine,
bp 70°C (15 mm), the specific rotation of which is the same as that of the original starting material.

2. Notes
1. (S)-(−)-α-Methylbenzylamine (95.8% optical purity) and its (R)-(+)-enantiomer (93.4% opticalpurity) were purchased from Aldrich Chemical Company, Inc. and used without further purification.
CAUTION: These amines are toxic. Air must be excluded to prevent formation of carbonates.
2. 2-Methylcyclohexanone was purchased from Aldrich Chemical Company, Inc., and used without
further purification.
3. Methyl vinyl ketone, purchased from Aldrich Chemical Company, Inc., is dried over anhydrous
potassium carbonate for 0.5 hr. The now slightly-colored oil is filtered and distilled under a nitrogen
atmosphere at reduced pressure, bp 55°C (260 mm). The colorless center of the distillate is collected
over a few milligrams (ca. 0.05% concentration) of hydroquinone.
4. A 25 wt % solution of sodium methoxide in methanol (4.6 M) was purchased from Aldrich Chemical
Company, Inc.
5. Any acetic acid present is thus neutralized (a few drops are usually sufficient). Confirm that a basic
pH has been reached by testing a drop of the solution, removed by syringe.
6. Although a TLC test (silica gel Merck 60 F254, ethyl acetate/hexane 20:80 elution, UV and chromicsulfuric acid visualization) of this oil reveals only one spot (Rf 0.6), capillary GLC (Hewlett-Packard
HP-5, 25 m × 0.2 mm × 0.5 μm, 200°C) shows in addition to methyloctalone 3 (retention time, 10.9min), an 8% impurity (retention time, 11.7 min) which is probably the regioisomer 4.

A chemically pure sample of methyloctalone 3, [α]D20 −190° (ethanol, c 1.00) is obtained by preparative
GLC (3 m × ", 5% carbowax 20 M on Aeropak 30, 180°C, retention time 12.4 min) of a distillate
sample. The impurity has a 13.2-min retention time under these conditions. A good approximation of
the reaction ee is calculated as follows, taking into account the optical purity of the starting amine(95.8%) and the [α]D20 −219° (ethanol, c 1.00) value (Note 8) for optically pure methyloctalone 3: ee =100 × 190 × 100/95.8 × 219 91%.
7. If no crystalline mass is formed but instead an emulsion of the two liquid phases appears, the entire
solidification must be repeated (liquid nitrogen cooling).
8. Chiral capillary GLC (OV-1701 + trimeb/2), 25 m × 0.3 mm, He, 65 kPa, 130°C: (R)-(−)-3, 58.3 min(98%); (S)-(+)-3, 62.0 min (2%). Optically pure methyloctalone 3 is obtained by recrystallizing asample of the purified compound several times until a constant [α]D20 −219° (ethanol, c 1.00 or
methanol, c 1.10) is observed. As chiral capillary GLC shows only (R)-(−)-3, the [α]D20 −219°(methanol, c 1.1) value from the literature3 is confirmed.
9. If a pH lower than 12 is used, recovery of the amine is poor.

Waste Disposal Information
All toxic materials were disposed of in accordance with "Prudent Practices in the Laboratory";
National Academy Press; Washington, DC, 1995.

3. Discussion
Optically active methyloctalone 3 (or its enantiomer) has been obtained by resolution3,4 and byasymmetric synthesis.5 Both enantiomers are also available commercially. The synthesis described here
is by far the most simple and gives the best yield. It is an application of the general method reported forthe enantioselective elaboration of quaternary carbon centers through Michael-type alkylation of chiralimines.6 7 8 9 10 11 12 13 14This general method has the following advantages: very simple procedures, very mild conditions
involving moderate reaction temperatures and no acids, bases, catalysts, etc., allowing the use of labile
reactants, excellent regio- and enantioselectivities as well as high chemical yields, and creation of usefulchiral building blocks with quaternary carbon centers involving functionalized chains, allowing one todevise syntheses of natural compounds of various types (terpenes, steroids, alkaloids, etc.). As both
optically active amines are commercially available, targets with either desired absolute configuration
can be synthesized. Easy recovery of the auxiliary chiral moiety is possible.
Racemic methyloctalone 3 has been used as a starting material for many transformations as well as
for syntheses of racemic natural compounds. In the following examples, the absolute configuration of
the methyloctalone that would be required to obtain the natural enantiomer is indicated in parentheses:
β-gorgonene15 (S), widdrol16,17 (R), thujopsene16,18 (R), 7-hydroxycostal19,20 (R), β-selinene21,22 (R),costol, costal and costic acid21 (R), norketoagarofuran23,24 (R), β-eudesmol21,22,23,25 (R), taxane model26(S), polygodial27 (S), warburganal27 (S).
(R)-Methyloctalone 3 itself has been used to synthesize a pasmalinine model,28 a subunit ofpenitrem D,29 and several biologically active decalin derivatives.30
The following key-intermediates have been prepared by a procedure similar to the one describedabove, generally with excellent chemical and optical yields :The use of substituted acrylic acid derivatives shows that besides the high enantioselectivity usuallyobserved, the process is also highly diastereoselective, leading to compounds such as 27-32.

An acetylenic electrophile such as methyl propiolate leads to unsaturated compounds 35 and 36.
Linear β-ketoesters and lactones lead to compounds such as 37-39.

Compounds 40-45 arise from an analogous but intramolecular reaction. A special application of thechiral imine procedure, i.e., the use of an oxaziridine rather than an electrophilic olefin, yielding
compound 46, has been reported.

Several of these chiral non racemic compounds were used for the synthesis of bilogically active
products. Thus, (R)- and (S)-dimethyloctalones 5 lead respectively to natural and ent-geosmin.31 The(R)-enantiomer is also a precursor for the formal synthesis of isocostic and 3-isocostic acid32 while the(S)-enantiomer would lead to tuberiferine33 and was actually used to synthesize (−)-TMD, a specificinhibitor of the cholesterol biosynthesis.34 (S,S)-Dimethyloctalone 6 (a natural compound) leads to anatural octalin31 and would lead to α-vetispirene35 while the (R,R)-enantiomer would lead to
frullanolide.36 Compound 7 (R,R) is a precursor for the formal synthesis of muzigadial27 while the (S,S)enantiomer would lead to polygodial27 and warburganal.27 (+)-α-Cyperone 8 has been widely used as astarting material for the synthesis of many other sesquiterpenes37 and was in particular converted to entallohedycaryol.38 Compound 9 was transformed into a C2-symmetric chiral dione39 while compound 10
was the starting material for the synthesis of (−)-polywood.34 Tricyclic compounds 11 and 12 were used
respectively to synthesize a ring C aromatic steroid40 and a key [ABC] steroid intermediate41 while
compounds 13 were transformed into isosteres of aphidicolin as potential antiherpes agents.42
Methoxyketone 14 was converted to a precursor of bruceantin43 and compound 15 was used for the
preparation of a 14-hydroxymorphinan derivative.44 (R)-Ketoester 16 is a key building block for thesynthesis of (+)-cassiol,45 a potent antiulcerogenic agent, tridensone,46 and (−)-19noraspidospermidine,47 while 17 led to (+)-aspidospermidine.48 Compound 18 was converted to (−)nitramine.49,14 Lactams 19 show potent inhibition of the recombinant human type-1 steroid 5α-reductase.
Compound 20 was used to perform the first synthesis of (+)-petasine and (+)-isopetasine, potent
antiinflammatory and spasmolytic agents.50 Ketoester 21 is an intermediate for the formal total synthesisof vallesamidine.51 Ketodiesters 22 or 23 led to the marine antibiotic (−)-malyngolide.52 Azaheterocycles 24 were used to synthesize substituted isoquinoline derivatives which were evaluated as
potential inhibitors of 2,3-oxidosqualene lanosterol cyclase53 while oxo-heterocycles 25 and 26 havebeen used respectively for the synthesis of the mycotoxin, (−)vertinolide54 and of a subunit of marine
polyethers toxins55 as well as to advanced intermediates for the synthesis of the anti-fertility agent,zoapatanol.56 Compounds 32 and 34 lead to precursors of Vinca and Hunteria alkaloids.57 Ethylenic
compounds 35 and 36 were used respectively for the total synthesis of both riccardiphenols A and B58
and isocuparene.59 Acyclic compound 39 was converted to a nipecotic acid derivative.60 (R,R)-40 is acommon intermediate in the total synthesis of (−)-ajmalicine and (−)-tetrahydroalstonine61,62,63 as well asof (+)-yohimbine,64,62,63 (−)-ochropposinine,63 and (−)-emetine62,63 while (S,S)-40 leads to (−)-(10R)hydroxydihydroquinine.61,62,63
6566676869707172737475767778798081828384858687

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Appendix
Chemical Abstracts Nomenclature (Collective Index Number);(Registry Number)silica gel
petroleum etherbrine(S)-(−)-α-methylbenzylamine
β-gorgonene
widdrolthujopsene
7-hydroxycostal
β-selinene
costolcostalcostic acidnorketoagarofuran
β-eudesmol
polygodial
warburganalpenitrem D
isocostic and 3-isocostic acidtuberiferine(−)-TMDoctalinα-vetispirene
frullanolide
muzigadial(+)-α-Cyperone
ent-allohedycaryol
bruceantin(+)-cassiol
tridensone(−)-19-noraspidospermidine(+)-aspidospermidine(−)-nitramine
5α-reductase(+)-petasine(+)-isopetasine
vallesamidine(−)-malyngolide
2,3-oxidosqualene lanosterol cyclase
mycotoxin(−)vertinolide
zoapatanol
isocuparene(−)-ajmalicine(−)-tetrahydroalstonine(−)-ochropposinine(−)-emetine(−)-(10R)-hydroxydihydroquinine
ethanol (64-17-5)
potassium carbonate (584-08-7)hydrochloric acid (7647-01-0)

acetic acid (64-19-7)ethyl acetate (141-78-6)
methanol (67-56-1)
ether (60-29-7)
sodium acetate (127-09-3)
sodium hydroxide (1310-73-2)hydroquinone (123-31-9)
oxygen (7782-44-7)
nitrogen (7727-37-9)
sodium methoxide (124-41-4)
toluene (108-88-3)
Pentane (109-66-0)
magnesium sulfate (7487-88-9)
hexane (110-54-3)
methyl vinyl ketone (78-94-4)
2-methylcyclohexanone (583-60-8)
oxaziridine
methyl propiolate (922-67-8)(R)-(−)-10-METHYL-1(9)-OCTAL-2-ONE,
2(3H)-Naphthalenone, 4,4a,5,6,7,8-hexahydro-4a-methyl-, (R)- (63975-59-7)(R)-(+)-2-Methyl-2-(3-oxobutyl)cyclohexanone (91306-30-8)(+)-yohimbine
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