3-SUBSTITUTED SPECTINOMYCIN ANALOGUES AND THEIR PREPARATION

Abstract: Novel C-3′ analogues of spectinomycin and C-6′ ana­ logues thereof, including novel 3′-diazo-secospectinomycin compounds, can have antimicrobial properties.

Description: 3-SUBSTITUTED SPECTINOMYCIN ANALOGUES AND THEIR PREPARATION The present invention relates to 3-substituted analogues of the aminocyclitol antibiotic spectinomycin. Spectinomycin itself is illustrated herein as formula XX. The novel compounds of the present invention are C-3' analogues of spectinomycin and C-6' spectinomycin analogues, and also the corresponding 5'-desmethyl analogues, and those in which the hydrogen atoms attached to each of the nitrogen atoms bonded to C-l and C-3 in the molecules are replaced by a blocking group. The novel compounds include the C-6' analogues of spectinomycin, including the 5'-desmethyl analogue, which are compounds of the formula XXI. With respect to this formula, R3 is hydrogen; C2-8 alkyl; C1-4 haloalkyl, in which there are one, two or three halogen atoms; -R31-O-R32; or -R31-N-R33-R34; wherein R31 is C1-4 alkylene, R32 is hydrogen or C16 alkyl, R33 is hydrogen or C16 alkyl and R34 is hydrogen, 1-6 6 alkyl or a blocking group, with the proviso that no one combination of R31 and R32, R31 and R33 and R31 and R34 (when not a blocking group) contains more than 7 carbon atoms. EMI2.1 Unless otherwise qualified, reference herein to a C-3' analog or C-3' analogs of spectinomycin includes reference to the aforementioned analogs with the nitrogen atoms bonded to C-1 and C-3 blocked and to analogs of formula XXI (including analogs of formula XXI with nitrogen atoms bonded to C-i and C-3 blocked). Blocking groups as referred to above are sometimes called "protective groups in the art and are well known in many fields of organic chemistry, including peptide chemistry, fatty acid chemistry and especially semi-synthetic and synthetic antibiotic chemistry. Two commonly used blocking groups are carbobenzyloxy and t-butoxycarbonyl. Such groups can be removed easily and replaced by hydrogen atoms with suitable treatments, which may vary in detail depending on the particular blocking group and the particular molecule to which it is bonded, with acids or by reauction. A quite comprehensive list of blocking groups which can be attached to spectinomycin analogs is disclosed in U.S. Patent 4,173,647, the selection, preparation, use and hydrolysis of which is incorporated herein by reference. Regard lng the chemistry of adding and removing such blocking groups, see, e.g., Boissona, Adv. Org. Chem. 3, 159 (1963) and Windholz, et al., Tetrahedron Lett., 8, 2555 (1967). Spectinomycin itself is a known natural product. Bergy, et al., U.S. Patent 3,234,902. Numerous spectinomycin analogs in which the nitrogen atom bonded to C-i and C-3 are blocked are also known. Maier, et al., U.S. Patent 4,173,647; Federal Repulic of Germany Offenlegungschriften 2,756,912 (Derwent Farmdoc Accession No 50959B) and 2,756,913 (Derwent Farmdoc Accession No. 40960B). Numerous C-6' analogs, including the 5'-desmethyl, of spectinomycin as well as such analogs with nitrogen atoms bonded to C-1 and C-3 blocked, are known. U.S. Patent Application Serial No. 150,530, filed i6 May 1980. The present invention also concerns novel synthetic processes. In particular, it concerns: i) the novel, base-catalyzed synthesis of novel 3'-deoxo-3' diazo analogs of spectinomycin from known 3'-deoxo-3' arylsulfonylhydrazone analogs of spectinomycin; ii) the novel synthesis of novel 3'-deoxo-3'-(N,N'-dialkyl)¯ enamino-analogs of spectinomycin from novel 3'-deoxo 3'-diazo analogs thereof and (N,N-dialkyl )methyleneammonium halides in the presence of base in dry acetonitrile or other lower-alkyl-cyanide sol vents; iii) the novel synthesis of both 3'-(R)-spectinomycin cyanohyd rins and 3'-(S)-spectinomycin cyanohydrins from the corres ponding spectinomycins themselves (with keto-oxygen at C-3') and a source of cyano groups (e.g., hydrogen cyanide or ace tone cyanohydrin) in the presence of base or basic ion exchange resin; and iv) the novel synthesis of 3'-(S)-spectinomycin cyanohydrins from the corresponding 3'-(R)-spectinomycin cyanohydrins in the presence of base or basic ion exchange resin. With respect to novel process (iii), either epimer can be synthe- sized in excess of the other, depending on reaction conditions (especially reaction time, the base or Dasic ion-exchange resin used, and the concentration or amount thereof in the reaction mixture) 2S ze- scribed in greater detail below. Base catalyzes both hydrocyanation and isomerization at C-3 in novel process (iii). All of the analogs of the present invention which contain one or more blocking groups, and all of the analogs which contain a diazo group at C-3', are useful intermediates in processes for making C-3' analogs of spectinomycin which are useful as antimicrobial agents. The present invention also includes the pharmacologically acceptable acid addition salts of the novel antimicrobial C-3 analogs of spectinomycin disclosed herein. Similar to the known antimicrobial spectinomycin and C-6' spectinomycin-analog precursors, the novel C-3' spectinomycin analogs of the present invention, useful as antimicrobial agents, are either microbistatic or microbicidal. The novel antimicrobial C-3 spectinomycin analogs within the scope of the present invention are useful for inhibiting the growth of, or eliminating, microorganisms in various environments wherein the presence or unchecked growth of the microorganism is undesirable or harmful. Each of the antimicrobial C-3' spectinomycin analogs of the present invention is microbistatic or microbicidal against at least one microorganism in at least one environment in which the presence of the microorganism is undesirable or harmful. Microorganisms against which at least one of the antimicro bial C-3' spectinomycin analogs of the present invention are active include E. coli, K. pneumoniae, S. marcescens, S. typhi, S. faecalis, P. vulgaris, P. mirabilis, Ps. aeruginosa, as well as others, including both gram-negative and gram-positive bacteria. Some of the novel, antimicrobial C-3' spectinomycin analogs of the present invention are also useful for treating or preventing microbial infections in mammals, including humans. Other than well known deprotection reactions required to replace blocking groups with hydrogen atoms on blocked nitrogen atoms, the chemical transformations disclosed in the present specification occur at C-3'. None of the chemical transformations disclosed in the present specification alter the configuration at any chiral center, other than C-3', from the configuration exhibited by spectinomycin, its actinamine-ring-nitrogen-blocKed analogs, or any of the C-5' analogs of spectinomycin (including actinamine-ring-nitrogen-5locked) of concern in the present specification as starting materials in the synthesis of the novel C-3' analogs. Consequently, in many of the structural formulas used in the present specification, only the region of the structure near the C-3' position will be depicted. In such formulas, the portion of the structure not shown, including configurations at chiral centers not shown, is as in spectinomycin (formula XX) or the relevant C-6' analog thereof. The configuration about any chiral center that may be present in a blocking group or a substituent at C-6' is not changed by any of the chemical transformations disclosed in the present specification. Configurations at C-3' of the novel compounds disclosed herein are specified as either "R" or "S" in accordance with sequence rules well known to the art. Configurations about olefinic double bonds are specified using "E" to designate the trans-configuration and "Z" to designate the cis-configuration utilizing similarly art-recognized procedures for identifying geometric isomers. 2. Prior Art Several C-3' analogs of spectinomycin, with and without blocking groups on the actinamine-ring nitrogens (i.e., the nitrogens bonded to C-i and C-3) are known. In aqueous solution, spectinomycin exists as the C-3' ketone hydrate (formula XXII). Wiley, et al., J. Am. Chem. Soc. 85, 2652 (1963). Wiley, et al., J. Am. Chem. Soc. 85, 2652 (1963) also report the preparation of both C-3' epimers of 3'-dihydro-spectinomycin (formula XXIII). Knight and Hoeksema, J. Antibiotics 28, 136 (1975), disclose the h,N'-di(carDoDenzyloxy) aerivative of spectinomycin itself and both epimers of the 3'-dihydro analog. (The nitrogen atoms bonded to C-i and C-3 are designated herein as N and N', respectively.) Maier, et al., U.S. Patent 4,173,647, disclose both epimers of 3'-deoxo-3'-amino-3'-dihydrospectinomycin (formula XXIV) and a large number of actinamine-ring-nitrogen-blocked analogs of both including specifically the N,N'-di(carbobenzyloxy), N,N'-di(p-methoxybenzyloxycarbonyl), N,N'-di[(2,2,2-trichlorethoxy)carbonyl], and N,N'di(isobornyloxycarbonyl) analogs. The Maier, et al. U.S. patent also discloses a large number of actinamine-ring-nitrogen-blocked analogs of spectinomycin itself, including specifically the same five named above for the 3'-deoxo-3'-amino-3'-dihydro-epimers. The Maier, et al. U.S. patent also discloses numerous oximes and hydrazones of spec tinomycin and numerous actinarine-ring-ntrogen-blocked analcgs of spectinomycin. The patent discloses specifically spectinomycin benzyloxime and the N,N'-di(carbobenzyloxy) analog thereof, the iK,N'- di(carbobenzyloxy) analog of spectinomycin methyloxime, spectinomycin benzylhydrazone and spectinomycin acethydrazone. Numerous oximes and hydrazones of spectinomycin, and actinaminering-nitrogen-blocked analogs thereof, are also disclosed in Federal Republic of Germany Offenlegungschrift 2,756,912, published 5 July 1979 and abstracted at Derwent Farmdoc Accession No. 50959B. Methylsulfonylhydrazone and (p-tolyl )sulfonylhydrazone (i.e., tosylhydrazone) of spectinomycin and many of its N,N'-diblocked analogs are described in German Offenlegungschrift 2,756,912. Formula XXV shows the C-3'-region of spectinomycin hydrazone, a compound generically disclosed in U.S. Patent 4,173,647. Formula XXVI shows the C-3' region of spectinomycin tosylhydrazone. Maier, et al., in J. Antibiotics 34, 16 (1981), report information on the synthesis and biological activity of both C-3'-epimers of 3'-doxo-3'-amino-3'-dihydrospectinomycin, which is closely related to the disclosure of U.S. Patent 4,173,647. Woitun, et al., in J. Antibiotics 34, 22 (1981), a reference not necessarily subsequent to any invention disclosed herein, disclose numerous 3'-substituted amino analogs of 3'-deoxo-3'-(R)-3'-amino-3' dihydrospectinomycin and its N,N'-di(carbobenzyloxy) analog. The compounds disclosed in the Woitun, et al. reference which are closest to the subject matter of the present invention are illustrated by formula XXVII, wherein R27 is methyl, ethyl, isopropyl, n-pentyl, nnonyl, n-dodecyl or n-octadecyl, and formula XXVIII, wherein RZb is methyl or ethyl. Both compounds represented by formula XXVIII are reported in the Woitun, et al. reference to be inactive as antimicrobial agents. Hanessian, et al., in J. Antibiotics 34, 350 (1981), another reference not necessarily subsequent to any invention disclosed herein, disclose 3'-deoxo-3'-(S)-methylsulfonyloxy-N,N'-di(carbo- benzyloxy)-3'-dihydrospectinomycin and 3'-deoxo-3'-(S)-3'-azido-N,N'- di(carboDenzyloxy)-3'-dihydrospectinomycin (formula XXIX). Numerous analogs of both 3'-epimers of 3'-dihydrospectinomycin are reported in U.S. Patent Application Serial No. 020,073, filed 13 March 1979. The analogs include actinamine-ring-nitrogen unblocked and blocked with a wide variety of blocking groups, 5'-desmethyl compounds and compounds substituted at C-6' with a variety of substituents, including all the C-6' substituents within the scope of the present invention except the nitrogen-containing 6'-substituents in which the nitrogen atom is bonded to a blocking group. The C-3' region of compounds disclosed in U.S. Patent Application Serial No. 020,073, filed 13 March 1979, is displayed in formula XXX, wherein R includes hydrogen and alkyl of 1 to 8 carbon atoms, inclusive. Formula XXX is intended to indicate both the 3'-(R) and 3'-(S) stereoisomer of each analog. No analogs of spectinomycin appear known to the art wherein a halogen or carbon atom is bonded directly to C-3' or wherein a nitrogen atom, where present in a C-6' substituent, is bonded to a blocking group. Maier, et al., U.S. Patent 4,173,647; Federal Republic of Germany Offenlegungschriften 2,756,913 (Derwent Farmdoc Accession No. 509608) and 2,756,914 (Derwent Farmdoc Accession No. 50961B); and Maier, et al., J. Antibiotics 34, 16 (1981) teach the reduction of spectinomycin hydrazones (formulas XXV and XXVI) and oximes to both epimers of 3'deoxo-3'-amino-3'-dihydrospectinomycins. The references teach the presence of acid is advantageous in the reductions. Hanessian, et al., J. Antibiotics 34, 350 (1981), discloses reduction by precious metal-catalyzed hydrogenolysis of 3'-deoxo-N,N' di(carbobenzyloxy)-3'-(S)-3'-azido-3'-dihydrospectinomycin to 3' deoxo-3'-(S)-3'-amino-3'-dihydrospectinomycin. House, et al., J. Org. Chem. 33, 53 (1968), teach the formation of diazoacetic acid esters of unsaturated alcohols by the reaction of acetic acid tosy.hydrazone esters of unsaturated alcohols with triethyl amine in methylene chloride. In view of the known basesensitivity of spectinomycin and its analogs, as well as the significant structural and chemical differences between the C-3' region of 3'-arylsulfonylhydrazones of spectinomycin and its analogs and the carboxylate-carbon region of acetic acid arylsulfonylhydrazone esters, provide no basis to predicting whether the reaction conditions employed by House, et al., could be used to successfully form 3' deoxo-3 '-diazo-spectinomycin. There appear to be no examples of reactions between diazo ketones (e.g., in formula XXXI, the C-2'-C-3' region of 3'-deoxo-3'-diazospectinomycin), and (N,N-dialkyl)methyleneammonium halides prior to the disclosure herein of such a reaction used to link a carbon atom to the C-3' of spectinomycins by formation of 3'-deoxo-3'-(N,N-dialkyl)enamino-spectinomycins, which, as shown in the present specification, are valuable as intermediates in synthesis of antimicrobial 3'-analogs of spectinomycin. A review of hydrocyanation reactions of aldehydes and ketones, and the stereoselectivity thereof, is provided by Mathieu, et al., Formation of C-C Bonds, G. Thieme Publ. Stuttgart, W. Germany, Vol. I, pp. 429-440 (1973). See also Grewe, et al., Chem. Ber. 98, 104 (1965). In accordance with the disclosure herein hydrocyanation occurs at the C-3' ketone in spectinomycins under reaction conditions of novel processes (iii) described briefly above and in greater detail below. The prior art teaches that the 3'-(R)-spectinomycin cyanohydrins would be expected as the predominant products under such reaction conditions. Surprisingly and unexpectedly this kinetically favored product of the hydrocyanation, the 3'-(R)-spectinomycin cyanohydrin, is thermodynamically less stable than the 3'-(S)-epimer. The known spectinomycin analogs described herein, with the exception of the two compounds of formula XXVIII disclosed by Woitun, et al., J. Antibiotics 34, 22 (1981), for which no utility is described, are asserted in the various references cited to be useful as either antimicrobial agents or intermediates in processes for synthesizing analogs which are antimicrobials. All analogs which have blocking groups on the nitrogens bonded to C1- and C-3 in the actinamine ring, ana all 3'-hydrazone and 3'-oxime analogs, are described to be useful as such intermediates. The other analogs, other than the two of formula XXVIII disclosed in the Woitun, et al. reference, are disclosed to be useful as antimicrobials. The Invention 1. Summary of the Invention The present invention comprises: A) A compound of formula I, wherein R1 is (a) hydrogen or (b) a blocking group; wnerein R3 is (a) hydrogen (b) alkyl of 1 to 8 carbon atoms, inclusive, (c) -R3l-O-R32, wherein R31 is alkylene of 1 to 4 carbon atoms, inclusive, and R32 is hydrogen or alkyl of 1 to 6 carbon atoms, inclusive, with the proviso that the sum of the number of carbon atoms in Rj1 and the number of carbon atoms in R32 is less than or equal to 7, (d) µ-R31-NR33R34, wherein R31 is as defined above, wherein R33 is hydrogen or alkyl of 1 to 6 carbon atoms, inclusive, and R34 is hydrogen, alkyl of 1 to 6 carbon atoms, inclusive, or a blocking group, with the proviso that if Rd4 is not a blocking group, the sum of the number of carbon atoms in R31 and the number of carbon atoms in whichever of Rj3 or Rs4 has the larger number of carbon atoms is less than or equal to 7, or (e) alkyl of 1 to 4 carbon atoms, inclusive, substituted with 1, 2, or 3 halogen atoms; wherein A is (a) =N2, (b) &alpha;-H:ss-H, (c) a-H:ss-X, wherein X is chlorine or bromine, i.e., the configuration at C-3' is (R), (d) a-Cl : :-Cl, (e) =CH(NR5R6), with the proviso that (i) R1 is a blocking group and (ii) RS4 is not hydrogen and, if R33 is hydrogen, Rj, is a blocking group, and wherein R5 and R6, being the same or different, are alkyl of 1 to 6 carbon atoms, inclusive, and wherein the configuration at the vinylogous carbon bonded to C-3' is, with respect to C-2', E or Z, but not both, (f) a-CHO: :ss-H, i.e., the configuration at C-3' is (R), with the proviso that (i) R1 is a blocking group and (ii) R34 is not hydrogen and, if R33 is hydrogen, R34 is a blocking group, (g) methylene (=CH2), with the proviso that (i) R1 is a blocking group and (ii) Rj, is not hydrogen and, if R33 is hydrogen, RJ4 is a blocking group, (h) &alpha;-CH2OH:ss-H, i.e., the configuration at C-3' is (R), (i) &alpha;-H:ss-CH2NR5R6 or &alpha;-CH2NR5R6:ss-H, i.e., the configuration at C-3' is (R) or (S) but not both, (j) &alpha;-CH2: :ss-OH, i.e., the configuration at C-3' is (S), (k) epoxymethano (-O-CH2- or -CH2-O-), with the proviso that (i) R1 is a blocking group and (ii) R34 is not hydrogen and, if Rj, is hydrogen, Rd4 is a blocking group, (1) &alpha;-OH:ss-CH2N3 or &alpha;-CH2N3:ss-OH, i.e., the configuration at C-3' is (R) or (S), with the proviso that (i) R1 is a blocking group and (ii) Rd4 is not hydrogen and, if R33 is hydrogen, Rj4 is a blocking group, (m) a-OH:ss-(CH2)m-CN or &alpha;-(CH2)m-CN:ss-OH, wherein m is O or 1, i.e., the configuration at C-3' is (R) or (S), (n) &alpha;-OH:ss-(CH2)p-NR41R42 or &alpha;-(CH2)p-NR41R42: :ss-OH, wherein p is 1 or 2, and R41 and R42, being the same or different, are (i) hydrogen (ii) alkyl of 1 to 12 carbon atoms, inclusive, (iii) aryl of 6 to 12 carbon atoms, or (iv) aralkyl of 7 to 12 carbon atoms, inclusive, optionally substituted by one or two (1) fluoro, chloro or iodo, (2) -NR40R47, wherein R46 and R47 are hydrogen or alkyl of one to 6 carbon atoms. inclusive, being the same or different, (3) cyano, (4) hydroxy, (5) carboxy, (6) alkoxycarbonyl of 2 to 5 carbon atoms, inclusive, or (7) alkoxy of one to 4 carbon atoms, inclusive, (v) -R43-R44, wherein -R43- is a single bond or R43 is alkylene of 1 to 4 carbon atoms, inclusive, and R44 is cycloalkyl of 3 to 10 carbon atoms, inclusive, or R41 and R42 taken together with N form a heterocyclic amine ring with 3 to 10 carbon atoms, inclusive, in the ring, or (vi) -C0-R45, wherein R45 is (a) alkyl of one to 12 carbon atoms, inclusive, or aryl or aralkyl of 7 to 12 carbon atoms optionally substituted by one or two (1) fluoro, chloro or iodo, (2) -NRbRt+7, wherein R40 and R47 are hydrogen or alkyl of one to 6 carbon atoms, inclusive, being the same or different, (3) cyano, (4) hydroxy, (5) carboxy, (6) alkoxycarbonyl of 2 to 5 carbon atoms, inclusive, or (7) alkoxy of one to 4 carbon atoms, inclusive, (b) -R43-R44 wherein R and R44 are as defined above, or (c) pyridyl, piperazyl, pyrollyl or morpholinyl optionally substituted by (1) fluoro, chloro or iodo, (2) -NR46R47, wherein R46 and R47 are hydrogen or alkyl of one to 6 carbon atoms, inclusive, being the same or different, (3) cyano, (4) hydroxy, (5) carboxy, (6) alkoxycarbonyl of 2 to 5 carbon atoms, inclusive, or (7) alkoxy of one to 4 carbon atoms, inclusive; and wherein B1 is a-OH:ss-H and Bz is oxo, when A is =Nz or =CH(NRsR6), or B1 is a-Bs: :ss-H and Bz is a-B4:ss-OH wherein Bs and B4 are taken together to form oxa (-0-), when A is not =Nz or =CH(NR5R6); or the pharmacologically acceptable acid addition salts thereof when R1 and R34 are not blocking groups and A is not =N2. B) A process for preparing a compound of formula II wherein R1 and R3 are as defined above, which comprises: reacting in an inert organic solvent a compound of formula IIi wherein R4 is an aryl group, with an organic amine base. C) A process for preparing a compound of formula IV, wherein R7 is a blocking group; wherein Rd is as defined above; wherein R5 and Rb, being the same or different, are alkyl of 1 to 6 carbon atoms, inclusive; and wherein the configuration at the carbon atom to which -NR > Rb is bonded is, with respect to C-2', E or Z but not both, which comprises: reacting a compound of formula V, wherein R7 is as defined above, with a compound of formula VI, wherein X6 is chlorine or bromine, in the presence of a tertiary amine base in a solvent RbCN, wherein Rb is alkyl of 1 to 3 carbon atoms, inclusive. D) A process for C-3' stereoselectively preparing a compound of formula VII, wherein R1 and R3 are as defined above, such that said compound is present in an amount greater than the amount of the co-produced C-3' epimer thereof, which comprises: (a) combining a compound of formula VIII with a compound which is a source of cyano groups, in an unreactive organic solvent in the presence of base or basic ion exchange resin, and (b) isomerizing at the C-3' position of the compound of the reaction product of step (a) by allowing the reaction product to remain in the solution for a length of time sufficient to result in the formation of a mixture of the compound of formula VII with its C-3' epimer, characterized by an amount of the compound of formula VII which is greater than the amount of its C-3' epimer. E) A process for C-3' stereoselectively preparing a compound of formula X, wherein R1 and Rd are as defined above, such that said formula X compound is present in an amount greater than the amount of the C-3' epimer thereof, which comprises: (a) combining a compound of formula VIII with a compound which is a source of cyano groups, in an unreactive organic solvent in the presence of base or basic ion exchange resin, and (b) permitting reaction of step (a) to proceed in the solution for a length of time sufficient to result in the formation of compound of formula X, and (c) terminating the reaction of step (b) prior to the formation of an amount of said C-3' epimer which is larger than the amount of said formula X comoound by (i) quenching said reaction by the addition of acid to neutralize said base or said basic ion-exchange resin or (ii) removing said ion-exchange resin if no other base is present. F) A process for preparing a compound of formula VII wherein R1 and Rj are as defined above, from a compound of formula X which comprises: combining a compound of formula X with a base or a basic ion-exchange resin in an unreactive organic solvent. Bivalent substituents herein, e.g., A, B1 and B2 are defined, at least in part in the form a-Ri:B-Ris wherein R. represents the sub stituent in the alpha configuration and R represents the substituent J in the beta configuration with respect to the plane of the ring to which said substituent is attached. The term "aryl group" and "aralkyl group" in the definitions above are defined as is conventional in the art. See the discussion pertaining to the Charts. For convenience in assigning trivial names to compounds herein when B1 is a-B3:ss-H and B2 is a-B4:ss-OH, the chemical skeleton described when R1 is hydrogen and Rd is methyl in formula I shall be referred to as "secospectinomycin". The compounds within the scope of the invention are useful as either antimicrobial agents or intermediates and processes for synthesizing antimicrobial agents. The compounds within the scope of the present invention which are antimicrobial agents are the compounds of formula I wherein R1 and Rj4 are not blocking groups and A is not =Nz, and pharmacologically acceptable acid addition salts thereof. The compounds within the scope of the present invention which are useful as intermediates in synthetic processes to make the antimicrobial compounds of the invention are those of formula I wherein R1 or R34 or both R1 and Rj4, are blocking groups or A is =N2. The compounds within the scope of the invention which are useful as antimicrobial agents are microbistatic or microbicidal. They can be used to inhibit the growth of, or eliminate, microorganisms, including gram-negative and gram-positive bacteria, from environments in which the presence of microorganisms is undesirable or harmful. While the microbistatic or microbicidal potency of the antimicrobial agents within the scope of the invention will vary against any undesirable or harmful species of microorganisms in a particular environment, each antimicrobial agent within the scope of the invention will be useful against at least one species of microorganism in at least one environment in which the presence of members of the species is harmful or undesirable. Some of the antimicrooial agents within the scope of the invention are useful for treating or preventing microbial, especially bacterial, infections in mammals, including humans. It is contemplated that the antimicrobial agents within the scope of the invention wherein A is a-C1:B-C1, -H:ss-Cl and a-H:B-Br will not be useful for treating or preventing microbial infections in mammals. It is contemplated that most, if not all, of the other antimicrobial agents within the scope of the invention will be useful for treating or preventing microbial infections in mammals, including possibly humans. Whether an antimicrobial agent within the scope of the present invention is useful for treating or preventing microbial infections in mammals or not, it will nonetheless be useful for inhibiting the growth of, or eliminating, microorganisms from environments, other than mammalian systems, in which the presence of the microorganisms is undesirable or harmful. To be effective as microbistatic or microbicidal agents in an environment, the antimicrobial compounds within the scope of this invention must be introduced into the environment, by one of several means which are well known in the art and which are described in more detail below, in a quantity sufficient to inhibit the growth of, or eliminate, the target microorganisms. 2. Detailed Description of the Invention The illustrative examples below and Charts A to F describe the preparation and use of the novel compounds and processes herein. Variations from the details given herein, e.g., solvent or temperature or other reaction conditions, provided in the Examples and Charts, are also contemplated as part of the invention. The Examples and Charts are intended therefore to be illustrative, not comprehensive. Except as otherwise noted, however, the Examples do set forth preferred conditions for the reactions exemplified. Compounds of formula VIII in Charts A and F are the starting materials for synthesizing all compounds within the scope of this invention. All compounds of formula VIII, except those in which Rj4 within R, is a blocking group, are nown. For such starting materials see U.S. Patent Application Serial No. 150,530, filed 16 May 1980, the relevant disclosure of which is ,ncorporated here by reference. A blocking group can be incorporated into Rd (as Rut+) by employing the procedures exemplified in examples below for blocking the actinaminering nitrogens of spectinomycin with an unblocked or actinamine-ring nitrogen-blocked spectinomycin-analog starting material wherein R3 is an aminoalkyl or substituted aminoalkyl group. After this blocking reaction, wherein the starting material is unblocked, Rs4 will be the same as the blocking groups on the actinamine-ring nitrogens. If the starting-material spectinomycin analog is blocked before use in the reaction to block a nitrogen optionally present in R3, R3. can be optionally different from the blocking groups on the actinamine-ring nitrogens. As disclosed by Maier et al., U.S. Patent 4,173,647, and Federal Republic of Germany Offenlegungsschrift 2,756,912, the hydrazone or arylsulfonylhydrazone of formula XLII can be formed by well known methods for synthesis of hydrazones from ketones and hydrazine or aryl sul fonyl hydrazides, respectively. In Chart A, R60 is hydrogen or arylsulfonyl. The preferred route of synthesis of the formula XLIII diazo ketone is through an arylsul fonyl hydrazone intermediate. Chemical transformations of the formula XLII to formula XLIII compounds described in Chart A are undertaken in any organic solvent which is inert with the reactants and in which the reactants are soluble. For the formation of the formula XLIII diazo ketone from the formula XLII arylsulfonyihydrazone, such solvents include, for exampie, benzene, hexane, aimethyl ether, diethyl ether, tetrahydrofuran, unreactive chlorinated hydrocarbons such as methylene chloride and ethylene chloride, and the like. The preferred solvent is methylene chloride. The transformation of the formula VIII compound to the formula XLII I compound can be carried out at any temperature at which it proceeds at a rate acceptable to the person conducting it, at which reactants remain in solution in the solvent being employed, and at which reactants or products do not thermally decompose. Generally temperatures between OOC and 60 C are acceptaDle. Preferred temperatures are 20-30"C. Any organic anine base whicn is soluble in the solvent employed can be used in the reaction. The preferred base is triethylamine. Preferably the amount of base employed in the reaction is two tines the amount of arylsulfonylhyrazone employed R,, the aryl moiety on the arylsulfonyl groups, can be phenyl optionally substituted with one or two alkyl of 1 to 6 carbon atoms, inclusive, cycloalkyl of 3 to 8 carbon atoms, inclusive, or phenyl likewise optionally substituted by one or two alkyl of 1 to 6 carbon atoms, inclusive. Preferred are p-tolyl, m-tolyl, o-tolyl and phenyl. Especially preferred is p-tolyl. The reaction is carried out with nitrogen atoms in the spectinomycin moiety (other than at C-3') blocked or unblocked. Preferably the nitrogens are blocked, most preferably with carbobenzyloxy or t-butoxycarbonyl. In Chart B, Xo is chloro or bromo and Y is hydrogen or chlorine, provided that Y is chloro only when X70 is chloro. In Chart B, the diazo ketone of formula XLII I is blocked or unblocked at nitrogens other than those in the diazo group, except that, in the process leading to compound of formula LXXVII, the formula XLIII diazo ketone must be blocked. The preferred route to the compound of formula LXXVIII is to start with a diazo ketone of formula XLII I blocked with carbobenzyloxy. The preferred route to compounds LXXV or LXXIX is to start with a diazo ketone of formula XLII I blocked with t-butoxycarbonyl and proceed through the compound LXXVI intermediate. The starting materials, compounds V, XLV, LIII and LIV, in the processes illustrated in Charts C, D, and E are necessarily blocked with a blocking group on the actinamine-ring nitrogen atoms. "Blocking groups", including those optionally present on the nitrogen atom, if any, in the substituent on C-6', are selected from a large number of such groups well known from peptide chemistry. The list of such groups in columns 2 and 3 of U.S. Patent 4,173,647 includes all that can be used in the present invention as well as several (4-acetoxy- or 4-ethoxycarbonyloxybenzyloxycarbonyl, alkoxycarbonyl groups substituted with a furyl-(2)- or p-tolylsulfonyl group, a phenoxycarbonyl group substituted by a nitro gorup, and any dialkylaminooxycarbonyl group) that are not utilizable for the present invention. Those skilled in the art will readily recognize how to modify reaction conditions from those provided in the examples to add and remove blocking groups other than those for which conditions are specifically exernlified. In this specification, "blocking group" and "protecting group" are synonymous, as are "block" and "protect", and "deblock" and "deprotect". Preferred blocking group in all reactions within the scope of the present invention, except the sequences XLIII+LAXVI+LXXV and XLIII+LXXVI+LXXIX illustrated in Chart B, is carbobenzyloxy. In these two excepted reaction sequences, the preferred group is t-butoxycarbonyl. Except as otherwise noted herein, the deblocking steps indicated in the various Charts are required to obtain antimicrobially active compounds from blocked intermediates. In the Charts, compounds are not redrawn after the arrows indicating deblocking because deblocking simply replaces blocking goups on the nitrogen atoms to which they are bonded with hydrogen atoms and does not affect the molecules in any other way. Because deblocking does not affect substituents or configurations at C-3', redrawing structures after arrows indicating deblocking is superfluous. When deblocking leads directly to an acid addition salt, the free base can be generated from such salt by methods well known in the art, e.g., passing a solution of the salt in a solvent such as water, methanol, ethanol, tetrahydrofuran, 1,2-dimethoxyethane or the like through a basic ion exchange resin and collecting fractions of eluate which contain the free base. Pharmacologically acceptable acid addition salts can be produced from the free bases by methods well known in the art, e.g., neutralizing the free base in solution in a solvent such as water, methanol, ethanol, isopropanol, ether, 1,2-dimethoxyethane, p-dioxane or the like with any acid which has a pharmacologically acceptable conjugate base and then isolating the salt by filtration and direct crystallization or by evaporation of solvent followed by subsequent recrystallization from a suitable solvent. Acids which have pharmacologically acceptable conjugate bases include hydrochloric, hydrobromic, hydroiodic, sulfuric, phosphoric, maleic, citric, tartaric, fumaric, acetic, and the like. Especially preferred among the pharmacologically acceptable acid addition salts within the scope of the present invention is hydrochloric. The starting materials in the processes illustrated in Charts A, B, and F (i.e., compound VIII or compound XLIII) are optionally either without any blocking groups, with both actinamine-ring nitrogens blocked and any nitrogen atom optionally present in R unblocked, or with both actinamine-ring nitrogens and any nitrogen atom optionally present in Rj blocked. In tne process illustrated in Chart F, all steps are preferably carries ojt with carbobenzyloxy blocking groups on both actinamine ring nitrogens and the nitrogen atom, if any, present in R. If any of these nitrogen atoms is blocked, the blocking steps indicated will be necessary to produce an antimicrobial final product. If compound VIII in Chart F contains no blocking groups, all steps through synthesis of 3'-aminomethyl compounds LXIII and LXIV can be carried out. However, to proceed with reductive alkylation of compounds LXIII and LXIV, they must be blocked at both actinamine-ring nitrogens and the nitrogen atom optionally present in R. The preferred method for synthesizing compounds of formulas LXIII, LXIV, LXV and LXVI is the process illustrated in Chart F. The sub-processes in Chart D, LV+LXIX+LXXI and LVI+LXX+LXXII can be carried out in the same way as sub-processes LXVIII+LXIV+LXVI and LXVII+LXIII+LXV in Chart F, with possibly minor variations in reaction conditions, because of the additional methylene group in the compounds in Chart D, which would be readily ascertainable by one of ordinary skill. The formula LXXXVI I and LXXXVIII compounds of Chart F are prepared by acylation of N,N'-dibenzyloxycarbonyl-3'-aminomethyidShydro- spectinomycins (formulas LXIII and LXIV) by employing methods known in the art such as: (a) reaction with an acid anhydride, (b) reaction with an acid chloride in the presence of base, or (c) reaction with an acid and a coupling reagent such as dicyclohexylcarbodiimide or an alkylchloroformate. Preferred antimicrobial agents within the scope of the present invention are compounds of formula I wherein Rs is alkyl of 1 to 4 carbon atoms, inclusive, and A is a-OH:ss-CHzNHRbo or a-CHzNHRso:ss-OH, especially wherein the configuration at C-3' is (R) and wherein Röo is n-alkyl of 1 to 8 carbon atoms, inclusive, or (cyclohexyl)methyl. Especially preferred are such compounds wherein Rz is methyl. In the compounds of formula IV, the configuration at the vinylogous carbon bonded to C-3', with respect to C-2', is not known. However, the process (V+VI)IV illustrated in Chart C produces a compound stereospecifically at that position. Thus, the configuration is E or Z but not both. Similarly, in compounds of formula XLVI, the configuration at C-3' is not known, although it is known that the process IVXLVI illustrated in Chart C is stereospecific at C-3'. Thus, the compound of formula XLVI has configuration 3'-(S) or 3'-(R) but not both. Compounds of formula VI used in the process illustrated in Chart C are known or are easily synthesized on the basis of the teachings of Schreiber et al., Anger. Chem. (Int'l Ed., English) 10, 330 (1971) and Kinast et al., Angew, Chem. (Int'l Ed., English) 15, 239 (1976). It is important in carrying out the reaction (V+VI) that as little water as possible be present in the reaction medium. Thus, the solvent and amine base should be dry; the salts of formula VI and the compound of formula V should be as dry as possible, the reaction vessel should be dried before the introduction of reactants and the vessel should be flushed with a stream of unreactive, dry gas (e.g., N2) during the reaction. Those of skill in the art will be familiar with methods to minimize the amount of water in a reaction medium. The reaction (V+VI)IV can be carried out at any temperature at which reactants and products are soluble in the solvent used and stable and at which the reaction proceeds at an acceptable rate. A person skilled in the art will be able to ascertain temperature limits easily. Preferred temperature range is 20-30"C. Examples of tertiary amine bases that can be used in the process (V+VI)IV are provided above in the section on Summary of the Invention. Preferred is triethylamine. Preferred solvent is acetonitrile. The preferred method for making compounds of formula XLV is using the NaCA1HL(O(CHL),OCH,)21 reaction illustrated in Chart C. Rtj and RbL in Chart D and R6J and Rb4 in Charts D, E and F are the same as R41 and R4 defined above except that not both Rtj and Rb4 can be hydrogen. Unless otherwise specified, specific rotations reported in the examples are measure at room temperature, 24+2"C. Gram-molecular weights reported in the examples are determined by high resolution mass spectrometry using, when necessary, trimethylsilated compounds. The extent of silation is indicated for each example. A designation "(M+-Q)", wherein Q is the formula for a functional group or other molecular fragment indicates that the reported mass is determined from the mass of the molecular ion (M+) missing molecular fragment or function group Q. The compounds of formula I are useful either as intermediates in processes to synthesize antimicrobial agents or as antimicrobia agents. The compounds of formula I which contain one or more blocking groups or wherein A is =N2 are useful as intermediates in processes to synthesize compounds within the scope of the present invention which are antimicrobial agents. The compounds of formula I which contain no blocking group and wherein A is not =N2 are antimicrobial agents. The antimicrobial agents within the scope of the present invention inhibit the growth of, or eliminate, microorganisms in various environments where the presence of microorganisms is undesirable or harmful. The antimicrobial activity of compounds within the scope of the invention is determined by a serial-dilution technique whereby, for each of several species of microorganisms the minimum concentration of a compound required to prevent an increase in the concentration of cells in an inoculum containing a known initial concentration of cells in a growth phase is determined. Based on results with the technique applied to the known antibiotic, spectinomycin dihydrochloride, a compound is judged active against species of microorganisms if its "minimum inhibitory concentration" against the microorganism using the technique is less than 250 mcg/ml. By this criterion, all of the antimicrobial compounds within the scope of the invention were found to be active against at least one of the following species of microorganisms: S. aureus S. faecalis E. coli K. pneumoniae Ps. aeruginosa P. vulgaris P. mirabilis S. flexneri S. marcescens S. schottnuelleri. Minimum inhibitory concentrations (in mcg/ml) for several antimicrobial compounds within the scope of the invention are provided in the following Table: Compound A B C D E F S. aureus (UC&num;76) 7.8 62.5 31.2 3.9 3.9 40.25 S. faecalis (UCX694) 31.2-62.5 > 1000 7250 125 125 3.9 E. coli (UC445) 3.9-7.8 15.6 31.2 1.0 0.5 1.0 K. pneumoniae (UCr58) 2.0 7.8 3.9 1.0 1.0 3.9 Ps. aeruginosa (UCr95) 31.2 1000 > 250 31.2 62.5 7.8 P. vulgaris (UC&num;93) 7.8 250 62.5 3.9 15.6 31.2 P. mirabilis (UCi667) 3.9-7.8 62.5 62.5 7.8 7.8 62.5 S. flexneri (UC&num;143) 7.8-15.6 31.2 15.6 3.9 3.9 3.9 S. marcescens (UCE131) 3,9 62.5 15.6 1.0 1.0 7.8 S. schottnuelleri (UC&num; ;126) 15,6-31.2 > 1000 250- - - P. stuartii (UCA6570) > 250-1000 - - 15.6 15.6 12.5 A: Spectinomycin dihydrochloride pentahydrate (control) (Ranges reflect values obtained on different days) B: 3'-deoxo-3'-(R)-3'-bromo-spectromycin C: 3'(S)-3'-hydroymethyl-dihydrospectromycin D: 3'- (R)-3 '-aminomethyl-dihydrospectinomycin E: 3'-(R)-3'-(ethylamino)methyl-dihydrospectinomycin F: 3'-(R)-3'-[n-octylamino)methyl-dihydrospectinomycin Antimicrobial compounds within the scope of the present invention are active against E. coli and can be used, for example, to reduce, arrest and eradicate slime production in papermill systems caused by this microorganism. The antimicrobial compounds can also be used to prolong the life of cultures of Trichomonas foetus, Trichomonas hominis and Trichomonas vaginal is by freeing them of E. coli contamination. The antimicrobial compounds can be used to swab laboratory benches and equipment in mycological laboratories. The antimicrobial compounds can also be used effectively against K. pneumoniae. To be used as suggested above, the antimicrobial compounds of the present invention are incorporated into solutions, powders, suspensions, water-in-oil emulsions and like means of delivery which are well known and are described in greater detail below in connection with administration to mammals and humans. The concentration of antimicrobial compound in these means of delivery or application must be at least sufficient to inhibit the growth of target microorganisms at site of app1ication. These minium effective concentrations will vary, depending on the target microorganism, the environment in which its growth is to be slowed or it is to be eliminated, and the particular means of delivery used. The minimum effective concentration could be determined readily by a person skilled in the art. It is contemplated that the minimum effective concentration will range from about 1 part per million to about 10,000 parts per million, preferably 10 parts per million to 1000 parts per million in the solution, powder, suspension or emulsion. The preferred carrier is water. The antimicrobial compounds within the scope of the present invention, other than those wherein A is a-H:B-Br, a-H:ss-Cl, -Cl:-Cl, or a-CH2UH:8-H are useful for treating or preventing microbial infections, particularly bacterial infections, in mammals, including humans, suffering from or susceptible to such infections. The antimicrobial activity of a compound in mammals, including humans, is suggested by a minimum inhibitory concentration in the in vitro test described above of less than about 50 vg/ml against a microorganism. The antimicrobial activity of a compound against a microorganism in mammals, including humans, is ascertained more definitely by testing the ability of the compound to cure mammals, such as mice, rats or rabbits, which have been challenged with an acute dose of the microorganism. The compounds of formula I are also effective- for treating bacterial infections, such as gonorrhea, in mammals, including humans. The compositions of the present invention are presented for administration to humans and animals in unit dosage forms, such as tablets, capsules, pills, powders, granules, sterile parenteral solutions or suspension, eye drops, oral solutions or suspensions, and water-in-oil emulsions containing suitable quantities of the compound of formula I. For oral administration, either solid or fluid unit dosage forms can be prepared. For preparing solid compositions such as tablets, the compound of Figure I is mixed with conventional ingredients such as talc, magnesium stearate, dicalcium phosphate, magnesium aluminum silicate, calcium sulfate, starch, lactose, acacia, methylcellulose, and functionally similar materials as pharmaceutical diluents or carriers. Capsules are prepared by mixing the compound with an inert pharmaceutical ailuent and filling the mixture into a hard gelatin capsule of appropriate size. Soft gelatin capsules are prepared by machine encapsulation of a slurry of the compound with an acceptable vegetable oil, light liquid petrolatum or other inert oil. Fluid unit dosage forms for oral administration such as syrups, elixirs, and suspensions can be prepared. The water-soluble forms can be dissolved in an aqueous vehicle together with sugar, aromatic flavoring agents and preservatives to form a syrup. An elixir is prepared by using a hydroalcoholic (ethanol) vehicle with suitable sweeteners such as sugar and saccharin, together with an aromatic flavoring agent. Suspensions can be prepared with an aqueous vehicle with the aid of a suspending agent such as acacia, tragacanth, methyl-cellulose and the like. For parenteral administration, fluid unit dosage forms are prepared utilizing the compound and a sterile vehicle, water being preferred. The compound, depending on the vehicle and concentration used, can be either suspended or dissolved in the vehicle. In preparing solutions the compound can be dissolved in water for injection and filter sterilized before filling into a suitable vial or ampoule and sealing. Advantageously, adjuvants such as a local anesthetic, preservative and buffering agents can be dissolved in the vehicle. To enhance the stability, the composition can be frozen after filling into the vial and the water removed under vacuum. The dry lyophilized powder is then sealed in the vial and an accompanying vial of water for injection is supplied to reconstitute the liquid prior to use. Parenteral suspensions can be prepared in substantially the same manner except that the compound is suspended in the vehicle instead of being dissolved and sterilization cannot be accomplished by filtration. The compound can be sterilized by exposure to ethylene oxide before suspending in the sterile vehicle. Advantageously, a surfactant or wetting agent is included in the composition to facilitate uniform distribution of the compound. Additionally, a rectal suppository can be employed to deliver the active compound. This dosage form is of particular interest where the mammal cannot be treated conveniently by means of other dosage forms, such as orally or by insufflation, as in the case of young children or debilitated persons. The active compound can be incorporated into any of the known suppository bases by methods known in the art. Examples of such bases include cocoa butter, polyethylene glycols (Carbowaxes), polyethylene sorbitan monostearate, and mixtures of these with other compatible materials to modify the melting point or dissolution rate. These rectal suppositories can weigh from about 1-2.5 gm. The term "unit dosage form" as used in the specification refers to physically discrete units suitable as unitary dosages for human subjects and animals, each unit containing a predetermined quantity of active material calculated to produce the desired therapeutic effect in association with the required pharmaceutical diluent, carrier or vehicle. The specifications for the novel unit dosage forms of this invention are dictated by and directly dependent on (a) the unique characteristics of the active material and the particular effect to be achieved and (b) the limitations inherent in the art of compounding such an active material for use in humans and animals, as disclosed in detail in this specification, these being features of the present invention. Examples of suitable unit dosage forms in accord with this invention are tablets, capsules, pills, suppositories, powder packets, wafers, granules, cachets, teaspoonfuls, tablespoonfuls, dropperfuls, ampoules, vials, aerosols with metered discharges, segregated multiples of any of the foregoing, and other forms as herein described. An effective quantity of the compound is employed in treatment. The dosage of the compound for treatment depends on many factors that are well known to those skilled in the art. They include for example, tne route of administration and the potency of the particular compound. A dosage schedule for humans of from about 2 to about 4000 mg of compund in a single dose, administered parenterally or in the compositions of this invention, are effective for treating bacterial infections. More specifically, the single dose is from 5 mg to about 5000 mg in a single dose. More specifically, the dose is from about 10 mg to about 2500 mg of compound. 3. Examples The operation of the present invention is further illustrated by the examples below: Example 1 N,N'-dicarbobenzyloxyspectinomycin tosylhydrazone (Formula XLII: R60 is tosyl, R1 is carbobenzyloxy and Rd is methyl) Refer to Chart A. In 40 ml of absolute ethanol is dissolved 2.5 g (4.2 mmol) of N,N'-dicarbobenzyloxyspectinomycin (formula VIII) and 0.77 g (4.2 mmol) of p-toluenesulfonhydrazide. The reaction is stirred for 2 hr at room temperature under N2. At this time TLC shows no remaining N,N'-dicarbobenzyloxyspectinomycin. Removal of the solvent in vacuo affords 3.13 9 (98%) of title product as a white solid foam, which is used without further purification: CMR (d,-Acetone) 6 167.6, 153.4, 144.6, 137.9, 136.4, 130.1, 129.9, 129.0, 128.3, 97.3, 89.9, 74.7, 69.0, 67.2, 66.4, 66.0, 57.70, 57.5, 53.5, 33.2, 31.7, 31.4, 31.2 and 21.3. Example 2 N,N'-dicarbobenzyloxy-3'-deoxo-3'-diazosecospectino- mycin (Formula XLIII: R1 and Rd are as in Example 1) Refer to Chart A. In a 500 ml round-bottomed flask is dissolved 13.16 g (17.1 mmol) of N,N'-dicarbobenzyloxy-spectinomycin tosylhydrazone (Example 1) in 300 ml of CH2Cl2. To this solution is then added 2.4 ml (17.1 mmol) of triethylamine, The solution immediately turns yellow and is stirred under N2 for 5 hr. Removal of the solvent in vacuo affords 14.25 9 of crude title product as a yellow, brittle foam. The product is chromatographed on 1 kg of silica gel slurry-packed with ethyl acetate. The column is eluted with ethyl acetate. The elution sequence is a follows: 750 ml ethyl acetate, nil; 2450 ml ethyl acetate, 4.75 g of starting tosylhydrazone; 4900 ml ethyl acetate, 6.29 g of diazoketone. The yield of product based on recovered starting material is 94.2%. The product is obtained as a yellow solid: mp 84-90 (decomp); IR (KBr), 3450 (a), 2950 (m), 2100 (s), 1675 (s) cm.-1; PMR (CDClj) o 1.38 (CHdCH), 2.7, 3.1 (CH2), 3.1 (CH-N) 3.2 (CH-N, CH-O), 5.1 (anomeric, OCH2Ph) and 7.3 (aromatic); CMR (Acetone-d6) 189.5, 157.5, 138.0, 129.0, 128.2, 102.1, 92.2, 74.5, 73.8, 69.2, 67.9, 67.11, 64.2, 60.1, 59.8, 59.5, 59.3, 31.8, 31.7, 31.46, 31.3, 30.7, 29.8, 29.2, 28.8, and 20.9; Ea] = -25" (c, .7495, CHCl); UV (CHdCN) X (max) 297 (e=8181); M.S. no M+ observed. Anal. calc'd for C30H36O10H2: C 58.82, H 5.92; N 9.15; Found: C 55.84, H 5.79, N 7.03. When this reaction is repeated using 2 equivalents of triethylamine, N,N'-dicarbobenzyloxy-3'-deoxo-3'-diazospectínomycin is isolated in 75% yield. Example 3 N,N'-di-tert-butoxycarbonylspectinomycin (Formula VIII: R1 is tert-butoxycarbonyl and Rd is methyl) Refer to Chart A. In 700 ml of H20 contained in a 3g Morton flask with overhead stirrer and addition funnel is dissolved 200 g (0.40 mol) of spectinomycin sulfate tetrahydrate. To this solution is carefully added 64 g (0.80 mol) of NaHCO3 in batches. After stirring for 0.5 hr, 700 ml of t-butanol is added, followed by the addition of 176.6 g (0.81 mol) of di-t-butyl-dicarbon te is added over a period of 15 min. The reaction is then stirred for 65 hr at room temperature. The reaction is then transferred to a 4 1 separatory funnel and the aqueous phase is separated from the tert-butanol. The tert-butanol is removed in vacuo using a dry ice condenser under high vacuum. The residue consists of a gum which is taken up in 500 ml of ethyl acetate. The aqueous phase is concentrated and extracted with ethyl acetate (2 x 300 ml). All of the ethyl acetate solutions are combined and washed with water (1 x 500 ml). An emulsion forms which is broken up with the addition of 500 ml of brine. The aqueous wash is backwashed with 200 ml of ethyl acetate and the combined organics are washed with brine (2 x 500 ml) and dried over NazSO4. The solvent is removed in vacuo and the product is placed under high vacuum overnight to afford 131.38 g (62%) title product of a white solid. No residual tert-butanol is seen by C13 NMR. The title product is used without further purification: IR (CHC13) 3420, 1740 (s), 1675 (s), 1365 (s), 1255 (s), 1160 (s), 1130 (s), 1060 (s), and 885 cm-1; NMR (CDCl) 6 1.4 (CH3)3 C-0), 1.4 (CH3-CH), 2.0-3 (CH2C0, CHN's), 2.9, 3.0 (CH3N's), 3.1-5.0 (CH-O's); CMR 6 97.3, 91.8, 79.5, 75.1, 68.1, 66.3, 65.6, 60.4, 30.8, 29.8, 28.8, 28.5, 27.9,and 21.5; [&alpha;]D = -20 (C, 0.904, CHCl3). Anal. calc'd for C24H4oN201l: C, 54.13; H, 7.57; N, 5.26. Found: C, 52.8; H, 7.41; N, 4.76. Exact mass calc'd for CH64NzOllSi: 748.3818; Found: 748.3772. Example 4 N,N'-di-tert-butoxycarbonylspectinomycin tosylhydrazone (Formula XLII: Rbo and R3 are as in Example 1 and R1 is as in Example 3) Refer to Chart A. A solution containing 100 9 (0.19 mol) of N,N'-di-tert-butoxycarbonyl-spectinomycin and 35 9 (0.19 mol) of p-toluenesulfonhydrazide in 475 ml of absolute ethanol is stirred for 6.5 hr under N2 at room temperature. The solvent is removed in vacuo and the product is placed under high vacuum overnight. This affords 131 g (100%) of a white solid which is used without further purification. IR (KBr) 3500 (s), 2950 (s), 1650 (s), 1340 (s, broad), 1120 (s, broad), 1090 (s, broad), 925 (s) and 885 (s) cm 1; [&alpha;]D = -2 (C, 0.982, CHCl3); PMR (CDCl) 6 1.4 (tButyl), 2.8-3.0 (CHdN's), 3.4-4.8 (CH-O's), 7.3, 7.8 (aromatic). CHR (d6-Acetone) ô 153.7, 130.2, 129.8, 128.6, 97.4, 90.0, 79.6, 74.9, 69.1, 66.4, 57.7, 30.8, 30.7, 29.8, 28.9, 28.5, 27.9, 21.3 and 18.6. Anal. calc'd for C31H48N4O12S: C, 53.13; H, 6.90; N, 7.99; S, 4.58. Found: C, 51.85; H, 6.90; N, 7.67. Example 5 N,N '-di-tert-butoxycarbonyl-3 '-deoxo-3 '-diazo-secospec- tinomycin (Formula XLIII: R1, Rd and R6U are as in Example 4) Refer to Chart A. To a solution containing 50 g (71.3 mmol) of N,N'-di-tert-butoxycarbonyl-spectinomycin tosylhydrazone in 500 ml of CH > Cl2 is added 15 ml (107.6 mmol) of triethylamine. The solution turns yellow/orange and is stirred at room temperature under N2. During the course of the reaction an additional 10 ml (71.3 mmol) of triethylamine is added. After stirring for 8 hr at room temperature, the reaction is stored in the freezer overnight. The next morning the reaction is concentrated to a volume of 100 ml and chromatographed on 1.2 kg of silica gel which has been slurry packed in CH2Cl2 and then the column was eluted with ethyl acetate. Chromatography affords 33.0 g (85%) of N,N'-ditert-butoxycarbonyl-3'-deoxo-3'-diazospectinomycin as a yellow solid; IR (KBr) 3350 (s) 2850 (s), 2050 (s), 1625 (s), 1400 (s), 1325 (s), 1220 (s), 1125 (s), 1030 (s) and 885 (s) cm 1; CMR (d6-Acetone) 6 189.3, 102.17, 92.7, 79.32, 74.3, 69.1, 68.0, 67.1, 64.0, 59.7, 59.6, 59.2, 30.8, 30.6, 29.9, 29.2, 28.9, 28.6, 27.9 and 21.0; Ea]0 = -26 (C, 1.095, CHCld). Anal. calc'd for C24H40N4O10; C, 52.93; H, 7.40; N, 10.29. Found: C, 51.96; H, 7.25; N, 7.48%. Example 6 3 '-chloro-3 '-deoxospectinomycin via non-N-protected diazo spectinomycin intermediates (Formula LXXV: X7o is chloro and R3 is methyl) Refer to Chart B. A. To a solution of 3.0 g (6.06 mmol) of spectinomycin dihydrochloride pentahydrate in 25 ml of water is added a solution of 1.13 g (6.06 mmol) of p-toluenesulfonylhydrazide in 35 ml of absolute ethanol. The solution is stirred 22 hrs at room temperature and concentrated to dryness. The residue is dissolved in ethanol, concentrated to 20 ml and diluted with ether until cloudy and stored in the refrigerator. The resulting white powder is collected by filtration: yield 1.8 g of formula XLII (R7 is hydrogen) spectinomycin-3'-tosylhydrazone dihydrochloride: i aC NMR (CD3OD) o 176.0, 152.8, 145.4, 137.1, 130.6, 128.8, 97.7, 91.1, 71.9, 70.1, 67.6, 67.4, 63.0, 61.8, 59.6, 33.7, 31.9, 21.5, 21.4. B. A 200 mg (0.35 mmol) sample of the part A tosylhydrazone is suspended in 10 ml of dry CH2Clz with rapid stirring for 5 min. Triethylamine (0.19 ml, 1.40 mmol) is added resulting is dissolution of most of the solid and the formation of a bright yellow color. After 10 min, the solution is cooled to 0 and HCl gas is bubbled in, causing the yellow color to dissipate. The excess HCl is purged with an argon stream and the solvent is removed in vacuo to give a white solid. A sample is silyllated with 1:1 dimethylformamide/hexamethyldisilizone at soa for 30 min and analyzed by GC-MS on an OV-17 column. This analysis shows the product to be a mixture (ca. 1:1) of spectinomycin and the desired 3 '-chloro-3 '-deoxospectinomycin. The presence of the diazo ketone in the yellow solution is further demonstrated by infrared spectroscopy. A drop of the solution is concentrated on a salt plate and the infrared spectrum obtained. A strong bond at 2101 cm 1 is observed, showing the presence of the diazo group. This band is absent in the starting material and is also eliminated by treatment with acid (N2 evolution observed). Example 7 N,N'-dicarbobenzyloxy-3'-diazosecospectinomycin via hydrazone oxidation (Formula XLIII: Rd is methyl) Refer to Chart A. In 10 ml of CHCl is dissolved 500 mg (0.814 mmol) N,N'-dibenzyloxycarbonylspectinomycin hydrazone. To this solution is added 500 mg (5.75 mmol) of active MnO2. The resulting slurry is stirred for 24 hr at room temperature. The mixture is filtered through a pad of magnesium silicate and the filtrate is concentrated to dryness in vacuo to afford 258 mg of a yellow solid. The product is taken up in ethyl acetate and chromatographed on 20 g of silica, slurry packed in ethyl acetate. The column is eluted with ethyl acetate (2 L). In elution volume 0-200 ml there is obtained 180 mg of a mixture of title product and rearranged product. Elution volume 200-550 ml contains 63 mg of pure title product (12.6% yield) whose 13C-NMR is identical with that obtained from the treatment of N,N'-dibenzyloxycarbonylspectino- mycin tosylhydrazone with triethylamine. Example 8 N,N '-dicarbobenzyloxy-3 '-deoxospectinomycin (Formula LXXVII: R, and R1 are as in Example 1) Refer to Chart B. In a 500 ml round-bottomed flask is placed 29 g of zinc dust and 30 ml of 60:40 water/acetic acid. To this stirred zinc suspension is added 7.02 g (11.6 mmol) of Example 7 diazoketone. The solution is decolorized and N2 evolves. The reaction is stirred for 1 hr and is filtered. The filtrate is concentrated in vacuo to a thick liquid which is then partitioned between 100 ml of CHCld and 50 ml of water. The CHCld phase is separated and combined with two, 50 ml CHCld extracts of the aqueous phase. The combined CHClj extracts are washed with water (2 x 50 ml) and saturated aqueous NaHCOj (1 x 100 ml). The aqueous washes are backwashed with 50 ml of CHCld and the combined organic phases are washed with 100 ml of brine and dried over Na2SO4. Removal of the solvent in vacuo leaves 6.54 g of a white solid. Chromatography on 600 g of silica gel eluting with ethyl acetate affords 2.51 g of N,N'-dicarbobenzyloxy-spectinomycin and 3.03 g of a mixture containing the desired product. The mixture is rechromatographed on 100 g of silica gel and eluted with a methanol/CHClb gradient. This affords 1.03 g of pure 3'-deoxo-N,N'-di-carbobenzyloxyspectinomycin (15%): mp 126-1300 (decomp); IR(KBr) 3402 (s), 2950 (s), 1680 (s), 1450 (s), 1350 (s), 1170 (s), 1060 (s), 890 (m), 780 (m), and 710 (m) cm 1; CMR (d6-Acetone) ô 157.5, 157.4, 156.8, 138.13, 129.1, 128.3, 97.0, 90.7, 74.5, 72.6, 67.2, 66.4, 65.1, 60.2, 57.4, 36.2, 31.5, 30.7 and 21.41; NMR (CDCl3) O 1.2 (CHdCH), 1.4-2.0 (CH2-CH2), o 3.0 (CHdN), 3.5-4 (CH-O's) 5.1 (anomeric) 7.25 (aromatic); a]D = 260 (C 0.44, CHCld). Anal. calc'd for CdoHöNZOlu: C, 61.42, H, 6.53, N, 4.78; Found: C, 59.32; H, 6.32, N, 4.98. Example 9 3'-Deoxospectinomycin dihydrochloride (Formula LXXVIII: Rd is methyl.) Refer to Chart B. A 500 mg (0.85 mmol) sample of N,N'-di-CBz-3'-deoxospectinomycin (Example 8) dissolved in 30 ml of isopropyl alcohol is hydrogenated in the presence of 517 mg of a 10% Pd on BaS04 catalyst for 5 hrs at a pressure of 30 psi. TLC (thin layer chromatography) shows remaining N,N'-dicarbobenzyloxy-3'-deoxospectinomycin. An additional 237 mg 10 Pd/BaSO4 catalyst is added and the hydrogenation continues at 40 psi for 12 hrs. TLC shows only a trace of N,N'-dicarbobenzyloxy-3'-deoxo- spectinomycin. The reaction is filtered twice through celite and the filtrate acidified with 2i ml of 0.1N HCllisopropanol solution. Removal of the solvent in vacuo affords 255 mg of a light brown solid. The product is dissolved in water, filtered through a cotton plug and crystallized from aqueous acetone. After cooling for 1 hr at 50C, 85 mg of a white crystalline solid, pure title product, is collected (25.5 ). Mp 195-198 C (decom); IR (KBr) 3420 (s), 1450 (m), 1380 (m), 1175 (m), 1100 (m) and 1040 (s) cm 1; CMR (d6-Acetone) a 96.2 (d), 91.4 (s), 74.2 (d), 70.9 (d), 67.1 (d), 66.1 (d), 62.5 (d), 61.0 (d), 59.5 (d), 35.1 (t), 30.9 (q) 30.01 (t) and 21.1 (q). Exact mass calc. for C29H6óSi5Nz06 (penta-O-TMS): 678.3767; Found: 6783723. Example 10 3'-chloro-3'-deoxo-N,N'-di-tert-butoxycarbonyl spec tinomycin (Formula LXXVI: Rd and R7 are as in Example 3 and X7U is as in Example 6) Refer to Chart B. In 100 ml of CHzClz is dissolved 10.2 g (18.6 mmol) of N,N' di-tert-butoxycarbonyl-3'-deoxo-3'-diazo-secospectinomycin, Example 5. The solution is cooled to -70" (Dry Ice/isopropanol) under N2 and is treated with 143 ml of a freshly titrated 0.13 M HCl/CH2Cl2 solution. The addition takes 15 min and N2 is evolved. The solution is warmed to room temperature and an additional 20 ml of HCl/CHzCl2 solution is added. After warming, the solvent is removed in vacuo to afford 9.29 g of an off-white solid. The material is dissolved in ether and chromatographed on 300 g of silica gel packed in ether. The column is eluted with 2 liters of ether followed by 2 liters of ethyl acetate. This affords 2.64 g (25%) of title product, 3'-chloro-3'-deoxo-N,N'di-tert-butoxycarbonyl spectinomycin as a white solid. A 18C NMR shows the presence of only one isomer: IR (KBr) 3300 (s), 2900 (s), 1625 (s), 1440 (s), 1410 (s), 1330 (s), 1225 (s), 1125 (s), 1050 (br, s), 870 (s) and 600 (s) cm 1; CMR (d6-Acetone) 6 93.8, 90.5, 79.4, 74.9, 74.5, 74.4, 66.6, 66.4, 63.0, 60.6, 60.4, 39.2, 28.61 and 20.8; [a3D 180 (C, 1.006, CHCL3); PMR (d6-Acetone) 6 1.3 (CH3), 1.45 (t-Butyl), 1.7 (CH2's) 3.0 (CHdN's), 3.2-4.7 (CH-O's) and 4.96 (CH-02). Exact mass calc'd for tri-O-TMS derivative: C3H65ClN2O10Sij: 768.3635 Found: 768.3679 Example 11 3#-bromo-3'-deoxo-N,N'-di-tert-butoxycarbonyl spectino mycin (Formula LXXVI: X7U is bromo and R1 and Rd are as in Example 3) Refer to Chart B. In 50 ml of CH2C12 is dissolved 10.2 g (18.6 mmol) of N,N'-ditert-butoxycarbonyl-3 '-deoxo-3 '-diazo-secospectinomycin, Example 5. The solution is cooled to 0 in an ice bath and treated with 210 ml of a freshly titrated 0.087M HBr/CH2Cl2 solution (18.6 mmol). Nitrogen is evolved during the addition. At the completion of the addition, the reaction is stirred for 2 min, until the evolution of Na had ceased and the solvent was immediately removed in vacuo to afford 10.1 g of an off-white solid. The product is dissolved in methanol and adsorbed on silica gel. The dry silica gel was then placed on top of a column which had been slurry-packed in ether. The column was then eluted with ether and afforded 4.78 g (43%) of title product, 3'bromo-3'-deoxo-N,N'-di-tert-butoxycarbonyl spectinomycin as a white solid. A 13C NMR shows the presence of only 1 isomer. IR (KBr) 3400 (s), 2900 (m), 1640 (s), 1420 (s), 1350 (s), 1230 (s), 1130 (br, s), 1050 (s), 880 (s) and 770 (m) cm 1; CMR (d6-Acetone) 6 93.4, 89.4, 79.0, 74.2, 74.0, 73.8, 67.1, 66.1, 65.9, 60.0, 57.1, 57.0, 56.7, 56.6, 56.4, 55.9, 39.1, 28.0 and 27.3; a]D = +80 (C, 0.984, CHCl3). Exact mass calc'd for C33H65N2O10Si3br: 812.3131; Found: 812.3159. Example 12 3 '-deoxo-N,N '-di-tert-butoxycarbonyl-3 ' ,3 '-dichloro- spectinomycin (Formula LXXVI: X70 0 and Y are both chloro, R1 and Rd are as in Example 3) Refer to Chart B. In a 1-liter, three-necked round-bottomed flask equipped with addition funnel and thermometer is placed 150 ml of a 0.24M Cl2 solution in CC14 (36 mmol) and 180 ml of CH2Cl2. The solution is cooled to -70 (Dry Ice/isopropanol) and 10 g (18.4 mmol) of 3'-diazo-N,N'di-tert-butoxycarbonyl-3'-deoxo-secospectinomycin (Example 5) in 150 ml of CHZClz is added rapidly. N2 evolved during the addition. The reaction is stirred for 5 min after completion of the addition and the solvent is removed in vacuo immediately. This affords 11.16 g of a white solid. The product is dissolved in diethyl ether/CH2Clz and chromatographed on 250 g of silica gel slurry packed in diethyl ether. The column is eluted with ether to afford 4.31 g of a white solid which still contains an impurity. Trituration with ether affords 1.77 g of pure material. The mother liquors are concentrated and chromatographed on 100 g of silica eluting with 1 methanol/CHClj to afford an additional 2.08 g of pure material. This is combined with the triturated material to give 3.85 g of title product 3'-deoxo-N,N'-ditert-butoxycarbonyl-3',3'-dichlorspectinomycin as a white solid; (35) IR (KBr) 3350 (s), 2900 (s), 1625 (s), 1450-965 (br, strong), 915 (s), 870 (s), 795 (s) and 760 (s) cm 1; CMR [d6-Acetone) 6 94.6, 92.5, 79.5, 74.5, 68.4, 67.0, 66.6, 66.5, 60.8, 50.4, 28.7 and 20.32; [a]0 = +10 (C, 1.05, CHC13). Exact mass calc'd for C3sH64N2 10ClZSi3 802.3245; Found: 802.3270. Example 13 3'-chloro-3'-deoxospectinomycin dihydrochloride (Formula LXXV: Rd is methyl and X70 is chloro) Refer to Chart B. In 1 liter of CH2Cl2 is dissolved 2.0 g (3.6 mmol) of 3'-chloro3'-deoxo-N,N'-di-tert-butoxycarbonyl-spectinomycin, Example 10. The solution is cooled to 0 in an ice bath and anhydrous HCl is bubbled through the solution for 1 min. The reaction turns cloudy and is stirred for 1 hr at 00. Removal of the solvent in vacuo affords 1.82 g of a light yellow solid. The product is crystallized from aqueous acetone to afford 586 mg of a white crystalline solid. The mother liquors are lyophilized and the residue crystallized from aqueous acetone to afford an additional 302 mg of product. The total yield of crystallized product is 888 mg (58%): mp 211-220 (dec); IR (KBr) 3500 (s), 1600 (br, m), 1450 (m), 1380 (m), 1175 (s), 1075 (s) 1040 (s) and 925 (m) cm 1; CMR (d6-Acetone) 6 95.9, 93.6, 73.6, 70.9, 69.8, 69.6, 65.2, 64.2, 63.8, 62.0, 41.0, 34.5, and 23.2; [a]0 = +llu (C, 0.828, H20). Exact mass calc'd for C20H65CIN2O6Si6: 712.3377; Found: 712.3360. Example 14 3'-bromo-3'-deoxospectinomycin dihydrochloride (Formula LXXV: Rd is methyl, X70 is bromo) Refer to Chart B. In 1.2 liters of CH2Cl2 is dissolved 3.0 g (5.0 mmol) of 3'-bromo-3'-deoxo-N,N'-di-tert-butoxycarbonyl-spectinomycin, Example 11. The solution is cooled to 0 C and anhydrous HCl is bubbled through for 1 min. The reaction turns cloudy and is stirred for 1 hr and 10 min at 00. Removal of the solvent in vacuo left 2.71 9 of a white solid. The mother liquors all are lyophilized to afford 1.56 9 of a white fluffy solid: CMR (d6-acetone) 93.47, 90.6, 71.0, 69.34, 67.5, 67.0, 62.6, 61.2, 59.5, 54.3, 38.9, 31.9, 31.8 and 20.5; [a]0 70 (C, 0.5900, water). Example 15 3',3'-dichloro-3'-deoxospectinomycin dihydrochloride (Formula LXXIX) Refer to Chart B. In 700 ml of CHzCl2 is dissolved 3.0 9 (5.1 mmol) of dichloride 3'-deoxo-N,N'-di-tert-butoxycarbonyl-3,3'-dichlorspectinomycin, Example 12. The solution is cooled to 0 in an ice bath and anhydrous HCl gas is bubbled through for 1 min. The reaction mixture turns cloudy and is stirred for 1 hr at 00. Removal of the solvent in vacuo leaves 2.44 g of a white solid. The product is dissolved in 150 ml of water and is crystallized by the addition of 1400 ml of acetone. The solution is cooled for 1 hr and the product collected by vacuum filtraton. The first crop amounts to 856 mg of a white crystalline solid. The mother liquors are lyophilized and the lyophilized material is recrystallized from acetone/water to afford an additional 430 mg of product. Finally, the mother liquors are lyophilized to afford 625 mg of a white solid. The total yield of crystalline title product is 1.286 9 (55%): mp 240-250 (dec); IR (KBr), 3500 (s), 3000 (s), 1610 (m) 1450 (m), 1380 (m) 1170 (s), 1120 (s), 1060 (s), 930 (m), 805 (m) and 765 (m) cm 1; CMR (d-Acetone) 6 93.8, 92.7, 91.8, 70.5, 69.7, 68.5, 66.8, 62.4, 59.3, 49.3, 33.3, 31.90 and 20.1; [a]D= -100 (C, 0.9465, water). Exact mass calc'd for C29H64Cl2N2O6Si5 (penta-O-TMS): 746.2988; Example 16 3l-(Dimethylamino)methylene-N,N-dicarbobenzyloxy-seco- spectinomycin (Formula IV: R1 and R3 are as in Example 1 and R5 and R6 are methyl) Refer to Chart C. A 100 ml Morton flask is flame-dried under a stream of nitrogen. After cooling, the flask is charged with 2.0 g (21.4 mmol) of N,Ndimethylmethylene ammonium chloride (formula VI: R5 and R6 are methyl and X6 is cnloro) and 50 ml of acetonitrile. To this suspension is added 1.7 ml (23.1 mmol) of dry Et3N followed by 5.0 g (8.2 mmol) of N,N '-dicarbobenzyloxy-3 '-deoxo-3 '-diazo-secospectinomycin (Example 2). The solution is stirred for 4.5 hr at room temperature under nitrogen. During this time a slow evolution of nitrogen is observed, the yellow color of the starting material fades and a white precipitate forms. The reaction mixture is filtered and the filtrate concentrated in vacuo to afford 6.73 g of a yellow solid. The product is taken up in CHClj and chromatographed on 250 g of silica slurry packed in CHCl3. The column is eluted with an acetone/CHClj gradient as follows with 50-ml fractions being collected: 500 ml, 10% acetone/CHCl3; 500 ml 20; acetone/CHCl3, 5 liter 30% acetone/CHCl3 and 1 liter 401 acetone/ CHCl. Fractions 50-133 contain title product. These fractions are pooled and the solvent is removed in vacuo to afford 3.14 g (60%) of product: 13C-NMR (d6-Acetone) 6 190.0, 154.1, 138.2, 129.1, 128.3, 128.0, 102.6, 99.4, 91.6, 74.5, 69.7, 68.1, 67.9, 67.2, 60.1, 43.6, 33.3, 31.8, and 21.4; 1H NMR (CDCl3) 6 1.32 (CH3CH, d, J=6Hz) 3.11 (N-CHb's) 3.3-4.4 (OCH, NCH), 5.1 (anomeric, OCH2Ph) 7.25 (aromatic) and 7.7 (=CH-N(CH)z); [&alpha;]D +64 (C, 0.998, CHCl3); UV max (EtOH) 204 (E, 22150) and 338 (e 17,500); IR (CHCL3) 3439 (m), 3009 (m), 2905 (m), 1691 (s), 1652 (m), 1539 (s), 1485 (s), 1453 (s), 1421 (s), 1385 (s), 1343 (s), 1268 (s), 1171 (s) and 1024 cm 1. Exact mass calc'd for C39H57N3O9Si2 (tri-C-TMS - TMSOH): 767.3633; Found: 767.3648. Example 17 N,N'-dicarbobenzyloxy-3'-dioxo-3'-formylspectinomycin (Formula XLIV: R1 and R3 are as defined in Example 1) Refer to Chart C. To a solution containing 1.0 g (1.6 mol) of Example 16 product in 25 ml of tetrahydrofuran is added 1.6 ml of 1N HCl. The reaction is stirred at room temperature for 2 hr. The tetrahydrofuran is then removed in vacuo and the residue partitioned between CHC13 and water. The CHClz is separated and combined with a 30-ml CHClJ extract of the aqueous phase. The combined extracts are washed with 25 ml of brine and dried by filtering through a cone of MgSO4. Removal of the solvent in vacuo affords 806 mg of a white solid. The product is dissolved in CH2Cl2 and chromatographed on 40 9 of silica, slurry packed in 1:1 ethyl acetate/hexane. The column is eluted with an ethyl acetate/hexane gradient as follows: 100 ml, 6:4 ethyl acetate/hexane, 100 ml, 7:3 ethyl acetate/hexane, and 1 liter, 8:2 ethyl acetate/hexane. Elution volume 315 ml to 405 ml contains 105 mg of a white solid which is a mixture of isomeric aldehydes by 1JC-NMR. Elution volume 450-630 ml contains 408 mg of pure product, N,N'-dicarbobenzyloxy-3'-deoxo-3'-formylspectinomycin as a white solid: 1:C-NMR (d6 Acetone) s 138.3, 129.2, 128.5, 96.4, 92.4, 74.5, 73.8, 73.7, 71.1, 67.3, 66.3, 65.4, 61.0, 60.5, 60.4, 57.9, 57.8, 57.4, 56.2, 31.7, 30.8 and 21.4; 1H-NMR (d-Acetone) Ï 1.25 (CH-CH), 1.8-1.9 (CH2, CH) 2.7 (CH-CHO), 3.1 (CH3N); 3.2 (CH3N). 5.1 (anomeric, OCH2Ph), 7.3 (aromatic) and 9.9 (CHO); IR (KBr) 3400 (s), 1650 (s), 1430 (s), 1380 (s), 1330 (s), 1150 (s), 1110 (s), and 1050 (s); rLa]0 = +230 (C, 0.969, CHCl). Exact mass calc'd for C39H59N2O11Si3: 815.3426; Found: 815.3444 (M+-CH). Example 18 N,N'-dicarbobenzyloxy-3'-deoxo-3'-(hydroxymethyl) spectinomycin (Formula XLVII: R1 and R3 are as in Example 1) In 10 ml of methanol is dissolved 200 mg (0.325 mmol) of N,N'-dicarbobenzyloxy-3'-dioxo-3'-formylspectinomycin, Example 17. To this solution is added 4 mg (0.105 mmol) of NaBH. The reaction was stirred for 40 min at room temperature and quenched with 5 ml of 5% aqueous NaHCO. The methanol is removed in vacuo and the residue partitioned between ethyl acetate (25 ml) and water (25 ml). The ethyl acetate is separated and combined with a 15 ml ethyl acetate extract of the aqueous phase. The combined extracts are washed with 20 ml of brine and dried over Na2SO4. After filtering, removal of the solvent in vacuo leaves 212 mg of a white solid. This product is dissolved in CH > ClZ and chromatographed on 40 g of silica slurry packed in 1:1 ethyl acetate/hexane. The column is eluted with 1 liter of 7:3 ethyl acetate/hexane to afford in elution volume 315-908 ml, 190 mg (95%) of pure N,N'-dicarbobenzyloxy-3'-deoxo-3'-(hydroxy-methyl)spectinomycin as a white solid: C-NMR (d6-Acetone) 6 129.2, 128.4, 96.9, 92.7, 74.9, 74.6, 74.4, 73.8, 71.6, 67.2, 66.6, 64.8, 62.6, 61.2, 61.1, 60.4, 57.9, 57.5, 45.2, 33.0, 31.6 and 21.5; 1H-NMR (d6-Acetone) 5 1.1 (CHdCH, d, J=6Hz), 3.02 (NCHdIs), 3.3-4.2 (N-CH, O-CH), 5.02 (anomeric, OCH2Ph), 7.25 (aromatic); IR (KBr), 3450 (s), 1650 (s), 1425 (s), 1325 (s), 1150 (s), 1125 (s), 1075 (s), 890 (m), 775 (m), 750 (m) and 700 (m) cm 1, [&alpha;]D = +17 (C, 0.700, CHCl3). Mass spec m/e 817 (tri O-TMS-CH), 750, 634, 495, 393, 359, 321, 305, 270, 216, 170, 108, 91 and 73. Example 19 3 '-deoxo-3 '- (hydroxymethyl )spectinomycin (Formula I: R1 is hydrogen, R3 is methyl, A is -CH20H:ss-H, 81 is &alpha;-B3;ss-H and B2 is &alpha;-B4; ss-OH where B3 and B4 are taken together to form oxa) Refer to Chart C. In 2 ml of methanol is dissolved 63 mg (0.102 mmol) of N,N' aicarboDenzyloxy-3l-deoxo-3'-(hydroxymethyl)spectinomycin. To this solution is added 75 mg of Pd black and 40 ml of formic acid. The mixture is stirred for 7 min, filtered and the solvent removed in vacuo. This affords 50 mg of a material containing some residual solvent. The material is dissolved in water and 2 ml of 0.1N. HCl is added. The sample is immediately frozen and lyophilized overnight. This affords 27 mg of title product as a white solid (62%): 13C-NMR (DzO)d 96.3, 93.2, 73.3, 71.3, 67.2, 66.6, 62.5, 61.7, 61.4, 59.5, 45.2, 32.8, 32.6, 31.9 and 21.2. Exact mass calc'd for C23H4yNzO75i3 (tri-O-TMS, M+-CH3): 549.2847; Found: 549.2855. Example 20 N,N'-dicarbobenyloxy-3'-deoxo-3'-methylenespctino mycin by reduction of title product of Example 16 with NaBH3CN (Formula XLV: R7 is as R1 in Example 1 and R3 is methyl) Refer to Chart C. In 10 ml of methanol is dissolved 2.0 g (3.1 mmol) of Example 16 product. To this solution is added a trace of bromcresol green indicator in methanol. The solution is adjusted to a pH 44 by the addition of 0.1N methanolic HCl and 65 mg (1.03 mmol) of NaCNBH3 in 1 ml of methanol is added. The pH is kept near 4 and the reaction stirred for 2.5 hr. The reaction is then quenched by the addition of 5 ml of saturated NaHCO3 and the methanol is removed in vacuo. The residue is partitioned between 20 ml of water and 20 ml of ethyl acetate. The ethyl acetate is separated and combined with a 10-ml ethyl acetate extract of the aqueous phase. The combined extracts are washed with 20 ml of brine and dried over Na2SO4. Removal of the solvent in vacuo affords 1.73 g of a blue solid. The product is dissolved in CHCld and chromatographed on 200 g of silica gel, slurry packed in CHCl3. The column is eluted with an acetone/CHCl3 gradient as follows: 400 ml 10% acetone in CHCl; 400 ml 20% acetone in CHCl3; 2 liter 30% acetone in CHCl; 1 liter 1:1 acetone/CHCl. Elution volume 1400-1650 ml contained 245 mg of over-reduced product. Elution volume 1750-2300 ml contains 439 mg of N,N'-dicarbobenzyloxy-3'-deoxo-3'-methylenespecti- nomycin, title product, as a white solid. Elution volume 3500 mlfinish contains 157 mg of amino compound 3'-deoxo-3'-(N,N-dimethylaminomethyl)-dihydrospectinomycin. The yield of desired methylene compound is 23; C-NMR (db-Acetone) a 146.0, 138.3, 129.1, 128.3, 112.1, 97.5, 92.1, 74.5, 74.0, 72.9, 67.2, 66.4, 65.2, 60.3, 57.8, 57.7, 57.5, 40.8, 31.6 and 21.3; 1H-NMR (CDCl3) 6 1.2 (CH3CH, d, J=6Hz), 2.0-2.5 (CH, CH2), 2.9 (NCHz's), 3.8-4.4 (CH-O, CH-N), 4.5 (CHz=), 5.1 (anomeric, OCH2Ph) and 7.2 (aromatic); IR (CHCl3) 3673 (w), 3587 (m), 3418 (s), 3009 (s), 2952 (s), 1682 (s), 1486 (s), 1454 (s), 1407 (s), 1386 (s), 1346 (s), 1264 (s), 1234 (s), 1167 (s), 1128 (s), 962 (m) and 918 (m) cm 1; [a]D = -6 (C, 1,042, CHCl3). Exact mass calc'd for C30H57O10N2Si2 (M+-CHb for the bis TMS deriv): 727.3026; Found: 727.3069. Example 21 N,N'-dicarbobenzyloxy-3'-deoxo-3'-methylenespectino- mycin and N,N'-dibenzyloxycarbonyl-3'-deoxo-3'-(N,N dimethylaminomethyl)-dihydrospectinomycin by sodium bis-2-methoxy aluminum hydride reduction of title product of Example 16 Refer to Chart C. A 300-ml 3-necked Morton flask is flame-dried under a stream of nitrogen. After cooling, the flask is charged with 5.0 g (7.79 mmol) of enaminone and 50 ml of freshly distilled anhydrous tetrahydrofuran. To this solution is then added 2.4 ml of a 3.5M solution of Na[AlH2 (OCH2CH2OCH3)2] in toluene, via syringe over a period of 15 min. A vigorous evolutoin of gas is observed. At completion of the addition, TLC shows a complete loss of starting material. The reaction is then quenched by adding 100 ml of water and 100 ml of ethyl acetate. The entire mixture is then poured into 300 ml of ethyl acetate. The aqueous phase is separated and combined with 2, 100 ml water washes of the ethyl acetate. The combined aqueous washes are re-extracted with ethyl acetate (2 x 50 ml). The combined ethyl acetate extracts are washed with 200 ml of brine and dried over NaSO4. After filtering, the solvent is removed in vacuo to afford 4.89 g of a white solid. The product is taken up in CHCl3 and chromatographed on 300 g of silica, slurry packed in CHCl. The column is eluted as follows: 4 L 1% methanol/CHCl; 4 L 1.5% methanol/CHCl3; 6 L 2% methanol/CHCl3; and 2 L 10% methanollCHCl. The first 3 L of eluant are collected and then 50 ml fractions are taken. In elution volume 5.25 g to 9.45 g there appears 1.75 g (36% of theor.) of the title methylene compound. In elution volume 9.5 L to the finish, i.954 g of mixture of methylene compound and amino compound is obtained. Example 22 N,li'-dicarbobenzyloxy-3'-(hyoroxymethyl)Åaihydro- spectinomycin (Formula XLIX: R3 and R7 are as in Example 20) Refer to Chart D. In 2 ml of acetone is dissolved 178 nig (0.30 mmol) of N,N'dicarbobenzyloxy-3'-deoxo-3'-methylenespectinomycin, Example 21, 30 mg (0.114 mmol) of Et4NOAc#4H2O and 66 l (0.485 mmol) of 70% aqueous tBuOOH. The solution is cooled to 0 and 152 l of 2.5% 0504 in tertbutyl alcohol is added. The solution is stirred for an additional 4.5 hr and is quenched with the addition of 2 ml of 10% aqueous NaHSO3 and 2 ml of ethyl acetate. This mixture is stirred for 15 min, poured into 20 ml of brine, and extracted with ethyl acetate (2 x 20 ml). The combined extracts are washed with 20 ml of brine and dried over Na2SO. The solvent is removed in vacuo to afford 171 mg of a brown solid. The product is dissolved in CHCls and streaked on two, 2000 silica gel preparative TLC plates. The plates are eluted with 10% methanol/CHCld and visualized under short UV light. The more polar UV active band on each plate is collected and eluted with ethyl acetate. This affords 46 mg (24t) of the title compound as a white solid: 13C-NMR (d6-Acetone) 6 138.2, 129.2, 128.5, 94.4, 93.9, 74.5, 73.9, 73.6, 67.4, 67.0, 66.6, 65.3, 61.3, 61.2, 61.1, 60.5, 57.9, 57.7, 57.5, 38.6, 31.8, 31.6 and 21.2. Example 23 3'-(hydroxymethyl)dihydrospectinomycin dihydrochloride Refer to Chart D. In 6 ml of methanol is dissolved 45 mg (0.071 mmol) of N,N'-dicarbobenzyloxy-3'-(hydroxymethyl)dShydrospectinomycin, Example 22. To this solution is added 57 mg of Pd black and 30 pl (0.75 mmol) of formic acid. The reaction is stirred for 12 min, filtered and the solvent removed in vacuo to afford 32 mg of material. The material is dissolved in water and 1.4 ml of 0.1N HCl is added. The solution is immediately frozen and lyophilized to afford 26 mg (83%) of a white solid: 13C NMR (D20) 6 93.8, 93.7, 74.5, 70.9, 68.4, 67.0, 66.8, 65.9, 62.4, 61.6, 59.3, 37.8, 32.5, 31.9 and 20.9; Mass spec. m/e 724 (M+ -1) 513, 437, 401, 309, 217, 206, 187, 165, 147, 129, 117, 94, 73, 55 and 43. Example 24 N,N'-dibenzyloxycarbonyl-3'-Åaeoxo-3'-(N,N-dimethyl- aminomethyl)spectinomycin (Formula XLVI: Rj, Rg, and R6 are methyl and R7 is as in Example 20) Refer to Chart C. A 25 ml two-necked round-bottomed flask is thoroughly dried under nitrogen. After cooling, the flask is charged with 1 g (1.55 mmol) of enaminone and 10 ml of anhydrous methanol, freshly distilled from Mg. To this solution is added 3.1 ml (3.1 mmol) of 1 N methanolic HCl followed immediately by 32.6 mg (0.52 mmol) of NaCNBH. The reaction is stirred for 15 min at room temperature and is quenched by the addition of 5 ml of saturated aqueous NaHCO. The methanol is removed in vacuo and the residue is partitioned between ethyl acetate and water. The ethyl acetate is separated and combined with one 20-ml ethyl acetate extract of the aqueous phase. The combined extracts are washed with 20 ml of brine and dried over Na2SO. The extracts are filtered and the solvent removed in vacuo to afford 972 mg of a white solid. The product is taken up in CHCl3 and chromatographed on 100 9 of silica, slurry-packed in CHCl. The column is eluted as follows: 200 ml 10% acetone in CHCl; 200 ml 20% acetone in CHIC13; 2 liter, 30% acetone/ CHCl3; 1 liter 5% methanol in CHC13; 10% methanol in CHCl. Elution volume 1450-3450 contained 329 mg of the title compound as a white solid. In elution volume 3500 ml-4000 ml there is recovered 369 mg of N,N'-dibenzyloxycarbonylactinamine. The yield of desired material is 33%: 13C-NMR (d6-Acetone) 6 138.0, 129.1, 128.4, 96.8, 93.1, 75.0, 74.7, 71.7, 67.2, 66.4, 64.7, 60.1, 57.3, 45.6, 39.9, 34.1, 31.7, 31.6, and 21.5; 1H-NMR (d6-Acetone) 6 1.1 (d, CHCH3, J=6Hz), 2.2 (N(CH3)2; 3.1 (NCHs's) 3.3-4.7 (OCH, NCH); 5.1 (anomeric, OCH2Ph) and 7.25 (aromatic); IR (CHCld-) 3427 (m), 3363 (m), 3003 (m), 2984 (m), 2955 (m), 2904 (m), 1686 (s), 1454 (s), 1404 (s), 1384 (s), 1343 (s), 1225 (m), 1163 (s), 1125 (s), 1061 (s), 1028 (s), 989 (m), 951 (m), 911 (m) and 694 (m). Exact mass calc'd for C4dH6gN301VSi3: 859.4290; Found: 859.4316. Example 25 3'-deoxo-31-(N,N-dimethylaminomethyl)spectinomycin trihydrochloride Refer to Chart C. In 5 ml of methanol was dissolved 100 mg (0.155 mmol) of N,N'-dibenzyloxycarbonyl-3'-deoxo-3'-(N,N-dimethylaminomethyl)spectrinomycin, Example 24. To this solution was added 100 mg of Pd" and 62 pl (1.55 mmol) of formic acid. The reaction is stirred for 1 hr at room temperature, is filtered and the solvent removed in vacuo to afford 90 mg of a glass. The material is dissolved in water and 4.6 ml (0.46 mmol) of 0.1N aqueous HCl is added. The solution is immediately frozen and lyophilized for 12 hrs to afford 72 mg (96%) of a white solid, title product: 13C-NMR (D20) 6 95.6, 92.2, 72.5, 70.8, 67.0, 66.4, 62.3, 61.1, 59.0, 57.5, 45.2, 44.2, 39.7, 33.6, 32.0, 31.9 and 20.9. Exact mass calc'd for C26H57N3O6Si3: 591.3555; Found: 591.3536. Example 26 N,N '-dibenzyloxycarbonyl-3 '-deoxo-3 '-methylene- spectinomycin oxide (Formula LI: R3 and R7 are as defined in Example 20) Refer to Chart D. In 10 ml of CH2Cl2 is dissolved 1.0 g (1.67 mmol) of N,N'-dibenzyloxycarbonyl-3 '-deoxo-3 '-methylenespectinomycin. To this solution is added 20 mg (0.075 mmol) of vandadium IV bis(2,4-pentanedionate)oxide, VO(acac)2 follwed by 2.56 ml of a 0.625 M solution of tert-butyl hydroperoxide in CHzCl2. The reaction is stirred 22 hr and 1 ml of tert-butyl hydroperoxide solution is added along with an additional 10 mg of VO(acac)2. The reaction is stirred for 5 hr at which time TLC shows complete reaction. The solution is then poured into 20 ml of 5% aqueous Na2SO3. The CH2Cl2 is separated and combined with one 20 ml CH2Clz extract of the aqueous phase. The combined extracts are washed with 20 ml of brine and dried over Na2SO4. The solution is filtered and the solvent is removed in vacuo to afford 1.07 9 of a brown solid. The material is dissolved in CH2Clz and chromatographed on 10 g of silica, slurry packed in 1:1 ethyl acetate/hexane. The column is eluted with 1 liter of 1:1 ethyl acetate. In elution volume 200-1000 ml there is obtained 800 mg (78%) of the title compound as a white solid: 13C-NMR (d6-Acetone) 6 138.2, 129.2, 128.5, 96.8, 90.8, 75.0, 74.6, 74.5, 69.5, 67.4, 66.5, 65.8, 61.2, 60.2, 59.3, 57.8, 57.5, 47.5, 38.4, 31.8 and 21.3. 1H-NMR (CDCl) a 1.2 (d, J=6Hz, CHCH3), 2.0-2.8 (CH2, CH), 3.1 (NCHj's), 3.4-4.8 (OCH, NCH), 5.2 (anomeric, OCH2Ph) and 7.3 (aromatic); IR (CHCl3), 3412 (m), 3004 (m), 1680 (s), 1477 (m), 1450 (s), 1404 (m), 1384 (m), 1343 (s), 1241 (m), 1164 (s), 1120 (s), 1061 (s) and 886 (m) cm-1; [alD = +30 (C, 0.9265, CHCl Exact mass calc'd for C39H59N2O11Si3 (m+-CH): 815.3426; Found: 815.3443. Example 27 N,N'-dibenzyloxycarbonyl-3'-azidomethyldihydro spectinomycin (Formula LII I: R3 and R7 are as in Example 20) Refer to Chart D. In 30 ml of 1:5 water/EtOH is dissolved 1.139 9 (1.85 mmol) of Example 26 product, 1.53 g (18.5 mmol) of KN1 and 1.0 g (18.6 mmol) of NH4Cl. The resulting solution is heated at 850 C for 20 min, cooled, and concentrated in vacuo. The residue is partitioned between 30 ml of ethyl acetate and 30 ml of water. The ethyl acetate is separated and combined with one 20 ml ethyl acetate extract. The combined extracts are washed with 15 ml of brine and dried over Na2SO4. The solution is filtered and the solvent removed in vacuo to afford 975 mg of a light yellow solid. The product is dissolved in CHClb and chromatographed on 40 g of silica, slurry-packed in CHCl3. The column was eluted as follows: 100 ml 1% methanol/CHCl 1 liter 2% methanol/- CHCl; 1 liter 10% methanol/CHCl. In elution volume 400-700 ml there is 427 mg of the title compound (35%): 13C-NMR (d6-Acetone) 6 138.1, 129.2, 128.8, 128.4, 94.5, 92.6, 75.3, 74.4, 73.8, 67.3, 66.4, 65.4, 61.2, 61.0, 60.4, 57.7, 57.6, 57.3, 55.7, 39.2, 31.5 and 21.1; 1H-NMR (d6-Acetone) 6 1.2 (d, J=6Hz, CHCH) 1.3-1.9 (CH2), 3.1 (NCH3); 3.54.8 (OCH, NCH); 5.1 (anomeric, OCH2Ph); 5.8 (CH2Nd) and 7.3 (aromatic); IR (CHClj) 3563 (m), 3450 (m), 3015 (s), 2978 (m), 2936 (m), 2112 (s), 1690 (s), 1485 (s), 1452 (s), 1406 (s), 1383 (s), 1344 (s), 1205 (s), 1169 (s), 1124 (s), 1108 (s), 1080 (s), 1056 (s) and 723 (s) cm 1; [a]D = -70 (C, 0.994, CHCl3). Exact mass calc'd for C39H605O11Si3 (M+-CH3) 858.3597; Found: 858.3578. Example 28 3-S-3 '-aminomethyldihydrospectinomycin trihydrochloride (Formula LXI: R3 is methyl) Refer to Chart E. In 5 ml of methanol is dissolved 100 mg (0.152 mmol) of N,N'dibenzyloxycarbonyl-3 '-azidomethyldihydrospectinomycin, Example 27. To this solution is added 100 mg of Pd and 61 ul (1.52 mmol) of formic acid. The reaction was stirred for 10 min, was filtered and the solvent is removed in vacuo to afford 79 mg of 3 clear glass. The product is taken up in water and 4.6 ml (0.46 mmol) of 0.1N aqueous HCl is added. The sample is frozen and lyophilized overnight to afford 62 mg (86%) of a white solid: 13C-NMR (D20) s 93.5, 92.6, 72.5, 70.6, 68.0, 66.8, 62.3, 61.1, 59.0, 44.4, 38.8, 32.1, 31.8 and 20.6. Example 29 N,N '-dibenzyloxycarbonyl-3'-(cyanomethyl )dihydro spectinomycin (Formula LV: R3 and R7 are as in Example 20) Refer to Chart D. In 100 ml of 1:5 water/EtOH is combined 1.0 g (1.62 mmol) of Example 26 product, 1.05 g (16.2 mmol) of KCN and 866 mg of NH4Cl. The reaction is stirred for 5 hr at room temperature, after which the reaction appears complete by TLC. The ethyl acetate is removed in vacuo and the residue partitioned between ethyl acetate and water. The ethyl acetate is separated and combined with one, 15-ml extract of the aqueous phase. The combined extracts are washed with 25 ml of brine and dried over NaSO4. After filtering, the solvent is removed in vacuo to afford 959 mg of a white solid. The product is taken up in CHCl3 and chromatographed on 100 g of silica, slurry packed in CHCl3. The column is eluted as follows: 1 L 1% methanol/CHCl3; 1 L 2% methanol/CHCl3; 1 L 3% methanol/CHCl3; 1 L 4X methanol/CHC13; 1 L 5% methanol/CHCl3; 2 L 10% methanol/CHCl3. In elution volume 1890 ml to 2835 ml there is obtained 254 mg of epoxide. In elution volume 3510 ml to 4410 ml there is obtained 156 mg of the title compound (19.7% yield based on recovered epoxide): 1jC-NMR (d6-Acetone) 6 138.2, 138.1, 129.2, 128.5, 118.2, 94.5, 92.1, 74.4, 74.2, 73.8, 73.7, 73.3, 67.3, 66.4, 65.7, 61.2, 61.1, 57.8, 57.7, 57.4, 57.3, 40.6, 31.7, 31.6, 24.9 and 20.9. Mass spec (di-ThS deriv) m/e 785 (M+) 512, 455, 299, 276, 247, 199, 149, 131, 116, 97, 85, 73 and 57. Example 30 3'-(cyanomethyl)dihydrospectinomycin dihydrochloride Refer to Chart D. In 2 ml of methanol is dissolved 37 mg (0.057 mmol) of N,N' dibenzyloxycarbonyl-3 '-(cyanomethyl )4ihydrospectinomycin. To this solution is added 50 mg of Pd followed by 23 vl of formic acid. The reaction is stirred for 2 min and is filtered. Removal of the solvent in vacuo affords 25 mg of a white solid. The product is dissolved in 10 ml of O.1N HCl and lyophilized to afford 28 mg of a white solid (100%). 13C-NMR (D20) 6 120.3, 94.0, 92.8, 73.7, 71.1, 68.7, 67.2, 62.7, 61.6, 59.4, 40.5, 32.4, 32.0, 25.5 and 20.9. Exact mass calc'd for CzbH59Nj07Si4 (tetra-TMS deriv): 661.3430; Found: 661.3407. Example 31 N,N'-dibenzyloxycarbonyl-3-(S)-3'-aminomethyldihydro spectinomycin (Formula LXI II: Rb and R7 are as in Example 20) Refer to Chart E. In a Paar hydrogenation bottle is combined 406 mg (0.63 mmol) of N,N'-dibenzyloxycarbonyl-3'-(S)-3'-(azidomethyl)dihydrospectinomycin (Example 27) and 404 mg of PtO2 and 10 ml of isopropanol. The solution is hydrogenated at 10 psi for 1.5 hr. The solution is then filtered through magnesium silicate and the solvent removed in vacuo to afford 367 mg of a title product as a solid. The product is taken up in 5% methanol/CHCl3 and filtered through 3 9 of silica with 100 ml of 10% methanol/CHCl3. Removal of the solvent in vacuo affords 273 mg of an off-white solid: 13C-NMR (d4-methanol) 138.1, 129.5, 129.0, 128.8, 94.8, 93.7, 74.7, 73.3, 68.3, 67.7, 66.8, 65.7, 61.2, 57.9, 46.9, 40.0, 31.8 and 21.2 ppm. Example 32 N,N'-dibenzyloxycarbonyl-3'-(R)-3'-aminomethyidinydro- spectinomycin (Formula LXIV: Rb and R7 are as in Example 20) Refer to Charts D and E. A. In 20 ml of methanol is dissolved 1.09 g (1.67 mmol) of N,N '-dicarbobenzyloxy-3 '-deoxo-3 '-methylenespectinomycin (Example 20) and 531 mg (5.0 mmol) of Na2COd, To this solution is added 0.2 ml of 30* H20z. The reaction is stirred at room temperature for 10.5 hr, at which time TLC shows complete reaction. The reaction is poured into 50 ml of water and extracted with ethyl acetate (2 x 30 ml). The combined extracts are washed with 30 ml of brine and dried over Na2SO4. After filtering, removal of the solvent in vacuo affords 1.027 g of a white solid. The product is taken up in CHzCl2 and chromatographed on 75 g of silica slurry packed in 1:1 ethyl acetate/hexane. The column is eluted as follows with 30 ml factions taken: 700 ml, 1:1 ethyl acetate/hexane; 2 1 6:4 ethyl acetate/hexane and 500 ml 7:3 ethyl acetate/hexane. Elution volume 990-1680 ml contained 503 mg of a white solid which contains ss-epoxide (Formula LI), approximately 1:1. Elution volume 1830 ml to 3090 ml contains 186 mg of pure a-epoxide (formula LII). (18% yield): 13C-NMR (d5-Acetone) 138.2, 129.1, 125.4, 96.4, 91.6, 74.9, 74.5, 69.6, 67.2, 66.4, 65.4, 60.5, 60.2, 57.5, 50.8, 38.1, 31.7 and 21.3. B. The formula LII a-epoxide of part A (90 mg, 0.146 mmol) is dissolved in 4 ml of ethanol and potassium azide (113 mg, 1.4 mmoi), ammonium chloride (53 mg, 1.0 mmol) and water (1.0 ml) are added. The mixture is stirred 5.5 hrs at SOC C under a nitrogen atmosphere, and then 16 hrs at room temperature. The solvent is then removed in vacuo and 50 ml of ethyl acetate and 5 ml of water are added. The organic layer is washed with brine and dried over magnesium sulfate. Removal of solvent in vacuo yields 93 mg (0.142 mmol, 97%) of N,N'-dibenzyloxycaroonyl-3'- (R)-3 '-azidomethyl-3 '-dihydrospectinomycin (formula LIV) as a white solid: 13C NMR (d6-acetone) 6 157.5, 138.5, 129.2, 128.7, 128.4, 95.0, 92.9, 76.6, 74.7, 74.4, 67.5, 67.3, 66.4, 65.5, 60.9, 57.7, 54.5, 39.9, 31.8, 21.5; IR (CHC13) 3576, 3381, 3065, 3006, 2936, 2908, 2469, 2189, 1484, 1406, 1384, 1282, 1240, 1221, 1025, 1000, 951, 912, 600 cm1; Rf = 0.47 (silica gel,¯10% methanol/chloroform). C. Azide of part B, (1.49 g, 2.27 mmol) is dissolved in 30 ml of isopropyl alcohol, 1.3 g of PtO2 is added and the mixture is hydrogenated at 10 psi for 2 hr. An additional 1.0 g of Pt02 is added and the hydrogenation is continued for an additional 2 hr. The mixture is filtered through diatomaceous earth and magnesium silicate and solvent is removed in vacuo to afford 960 mg of a brown solid. The product is chromatographed on 40 g of 230-400 mesh silica gel packed with 1% methanol/CHCl3 and eluted with 200 ml of 2% methanol/CHCls, 200 ml of 3% methanol/CHClj, 1 liter of 5% methanol/CHCld, 2 liters of 7% methanol/CHClj and the remainder 10X methanol/CHCl8, collecting 35 ml fractions. Fractions 88-126 are pooled on the basis of TLC to afford 370 mg (0.59 mmol, 26%) of title product as an off-white solid: 3C-NMR (methanol-d4) 6 159, 138.0, 129.4, 128.8, 128.6, 96.2, 94.2, 74.6, 73.6, 68.1, 66.7, 65.4, 60.7, 58.0, 45.5, 41.6, 31.7 and 21.5. Example 33 N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N-ethylamino methyl)dihydrospectinomycin (Formula LXVI: R3 and R7 are as in Example 20, R63 is ethyl and R64 is hydrogen) Refer to Chart E. In 5 ml of methanol is dissolved 591 mg (0.78 mmol) of N,N' dibenzyloxycarbonyl-3'-(R)-3'-aminomethyldihydrospectinomycin (Example 32). To this solution is added 0.43 ml (7.8 mmol) of acetaldehyde and a trace of methyl orange indicator in methanol. Then 16.3 mg (0.26 mmol) of NaCNBH in 1 ml of methanol is added. The pH is adjusted by addition of 1N methanolic HCl. The reaction is stirred for 1 hr and concentrated in vacuo. The residue is partitioned between water and ethyl acetate. The aqueous phase is made alkaline with concentrated NH,OH and the ethyl acetate is separated. The aqueous phase is extracted again with ethyl acetate (1 x 20 ml) and the combined extracts are washed with brine (1 x 30 ml and dried over MgSO4. After filtering, the solvent is removed in vacuo to afford 409 mg of a white solid, title product. The product is taken up in CHCls and chromatographed on 20 gm of silica, slurry-packed in CHCl3. The column is eluted as follows: 100 ml 1% methanol/CHCl3; 100 ml 2; methanol/CHCl; 100 ml 3% methanol/CHCl3; 100 ml 4% methanol/CHC13; 500 ml 5% metha nol/CHCl; and 500 ml 7% methanol/CHCl3. In elution volume 650-1000 ml there is recovered 123 mg of the title compound as a white solid: 1dC-NMR (d6-Acetone) 138.1, 129.1, 128.3, 128.1, 97.0, 93.8, 74.5, 71.6, 67.1, 66.4, 65.2, 57.6, 54.0, 44.4, 43.8, 31.6, 21.5 and 14.9 ppm. Exact mass calc'd for c34H77N3O11Si4 (tetra-TMS): 947.4635; Found: 947.4601. Example 34 N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N-octylamino methyl)dihydrospectinomycin (Formula LXVI: R3 and R7 are as in Example 20 and R63 is n-octyl and Rb4 is hydrogen) Refer to Chart E. In 5 ml of methanol are combined 500 mg (0.79 mmol) of N,N'-di benzyloxyCarbonyl-3'-(R)-3'-aminomethyidihydrospectinomycin, (Example 32) 1.23 ml of n-octanal and trace of methyl orange indicator. To this solution is added 16.5 mg (0.26 mmol) of NaCNBH3 in 1 ml of methanol. The pH is adjusted to 4 with 1N NCl/methanol and the reaction is stirred for 30 min. The reaction is concentrated in vacuo and the residue is taken up in ethyl acetate. The solution was washed with water (2 x 20 ml), combined with 1, 10 ml ethyl acetate backwash and washed with brine (1 x 30 ml). After drying over MgSo4, the solution is concentrated to an oil. The oil is taken up in CHCl3 and chromatographed on 33 g of silica, slurry packed in CHC13. The column is eluted as follows: 200 ml CHC13; 500 ml 1% methanol/CHCl3, 1 liter 2% methanol/CHCl3; 500 ml 3% methanol/CHCl3; and 500 ml 5% methanol CHCl3. Elution volume 900-1400 ml contains 165 mg of the title compound as a white solid: 3C-NMR (d6-Acetone) 138.2, 138.1, 129.1, 128.3, 97.0, 93.8, 74.6, 71.7, 67.1, 66.5, 65.2, 61.1, 57.6, 49.8, 44.5, 32.4, 32.1, 31.6, 30.8, 30.0, 27.8, 23.2, 21.5 and 14.3 ppm. Exact mass calc'd for C5UH86N30llSi4 (tetra-ThS-CH): 1016.5339; Found: 1016.5327. Example 35 3'-(R)-3'-(N-ethylaminomethyl)dihydrospectinomycin trihydrochloride Refer to Chart E. In 10 ml of methanol is dissolved 123 mg (0.19 mmol) of N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N-ethylaminomethyl)dihydrospectinomycin (Example 33). To this solution is added 123 mg of Pd black followed by 72 ml of formic acid. The reaction is stirred for 20 min, filtered and concentrated in vacuo to afford a white solid. The product is taken up in water and 1 ml of 1N HCl is added. The solution is frozen and lyophillized to afford 83 mg (89; yield) of title product, a white solid: 13C-NMR (D20) 94.0, 93.2, 73.2, 70.4, 68.2, 66.8, 66.2, 62.4, 60.5 59.3, 50.5, 45.1, 40.7, 31.9, 31.5, 21.0, and 11.1 ppm. Exact mass calc'd for 35H8N3O11Si6 (hexa-TMS): 823.4690; Found: 823.4665. Example 36 3-(R')-3'-(N-octylaminomethyl)dihydrospectinomycin trihydrochloride Refer to Chart E. In 5 ml of methanol are combined 153 mg (0.21 mmol) of N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N-octylaminomethyl)dihydrospectinomycin, (Exam (Example 34) and 153 mg of Pd black. To this mixture is added 80 ul (2.1 mmol) of formic acid. The reaction is stirred for 20 min, filtered and concentrated in vacuo to afford 124 mg of a white solid. The product is taken up in water and 1 ml of 1N HCl is added. The solution is frozen and lyophillized to afford 111 mg of title product a white solid (90% yield): 1dC-NMR (duo) 91.1, 89.2, 69.2, 66.5, 64.2, 62.8, 62.2, 58.4, 56.5, 55.3, 46.9, 45.7, 36.8, 28.3, 28.2, 27.8, 27.5, 25.4, 22.9, 21.9, 19.1, 17.0 and 10.5 ppm. Exact mass calc'd for C4lHy3Nd01lSi6 (hexa-TMS): 907.5629; Found: 907.5627. Example 37 N,N'-dibenzyloxycarbonyl-3'-(S)-3'-(N-ethylaminomethyl)- dihydrospectinamycin (Formula LXV: Rj and R7 are as in Example 20 and R63 and R65 are as in Example 33) Refer to Chart E. In 6 ml of methanol are combined 500 mg (0.774 mmol) of N,N'-dibenzyloxycarbonyl-3'- (S)-3 '-(aminomethyl )dihydrospectinomycin (Example 31), 44 ul (0.774 mmol) of acetaldehyde ana a trace of metnyl orange indicator in methanol. To this solutions is then added 16.2 mg (0.258 mmol, 0.774 mmol H ) of NaCNBH3 in 1 ml of methanol. The pH is adjusted with the addition of 1N methanolic HCl until the indicator is just pink. The reaction is then stirred at room temperature and additional 1N HCl/methanol is added to keep the indicator pink. After 2.5 hr the methanol is removed and the residue partitioned between water and ethyl acetate. The aqueous phase is made alkaline with 1N NaOH and the ethyl acetate is then separated. The aqueous phase is extracted again with ethyl acetate (2 x 30 ml). The combined organics are washed with brine (1 x 50 ml) and dried over MgSO4. After filter inge the solvent is removed in vacuo to afford 458 mg of a white solid. The product is taken up in CHCl3 and chromatographed on 20 gm of silica gel, slurry packed in CHClj. The column is eluted as follows: 100 ml, 1% methanol/CHCl3; 100 ml 2% methanol/CHCl3; 100 ml 3 methanol/CHCl3; 100 ml 5% methanol/CHCl3; 100 ml 7X methanol/CHCl3; and 700 ml 10% methanol/CHCl3. In elution volume 520-720 ml there is contained 306 mg of the title compound as a white solid (60% yield): 1bC-NMR (4 -Acetone) 138.1, 129.1, 128.3, 94.2, 74.4, 73.1, 67.2, 66.6, 65.1, 57.6, 57.5, 57.3, 55.7, 45.0, 40.3, 31.4, 21.1, and 15.3 ppm. Exact mass calc'd for C14H66N3O11Si3 (tri-0TMS,-CH: 860.4005; ExamPle 38 3'-(S)-3'-(N-ethylaminomethyl)dihydrospectinomycin trihydrochloride Refer to Chart E. In 10 ml of methanol are combined 294 mg (0.44 mmol) of N,N'-di- benzyloxycarbonyl-3'-(S)-3'-(N-ethylaminomethyl)dihydrospectinomycin (Example 37) and 200 mg of Pd black. To this solution is added 170 iil of formic acid. The reaction is stirred for 40 min and is filtered. Removal of the solvent in vacuo affords 225 mg of a white solid. The product is dissolved in 2 ml of water and 1.5 ml of 1N HCI is added. The solution is frozen and lyophillized to afford 215 mg of a white solid (97.5Z yield): 13C-NMR (D20) 96.3, 95.1, 75.5, 74.2, 70.6, 70.5, 70.3, 65.5, 65.0, 62.2, 54.5, 47.6, 41.7, 35.3, 34.6, 23.2 and 13.79 ppm. Exact mass calc'd for Cj5Hd1Nd07Sifi (hexa TMS): 823.4690 Found: 823.4690. ExamDle 39 N,N'-dibenzyloxycarbonyl-3'-(S)-3'-(N-butylamino methyl)dihydrospectinomycin (Formula LXV: R3 and R7 are as in Example 20 and R63 is butyl and R64 is hydrogen) Refer to Chart E. In 10 ml of methanol is dissolved 507 mg (0.803 mml) of N,N'-dibenzyloxycarbonyl-3'-(S)-3'-(aminomethyl)dihydrospectinomycin plc 31). To this solution is added 0.71 ml of n-butyraldehyde and a drop of methyl orange indicator in methanol. This is followed by the addition of 17mg of NaCNBHd in 1 ml of methanol. The pH is adjusted to 4 with the addition of 1N HCl/methanol. The pH is maintained at 4 for 0.5 hr while the reaction is stirred. The methanol is then removed in vacuo and the residue partitioned between ethyl acetate and water. The ethyl acetate is separated and combined with 1, 25 ml ethyl acetate extract of the aqueous phase. The combined extracts are washed with 50 ml of brine and dried over MgSO. After filtering, removal of the solvent affords 616 mg of a white solid. The product is taken up in CHCl6 and chromatographed on 30 g of silica gel, slurry packed in CHCl. The column is eluted as follows: 100 ml 1% methanol!CHCl3; 100 ml 2% methanol/CHCl3; 100 ml 3t methanol/CHCl3; 100 ml 4X methanol/CHCl3; 1.3 liter 5Z methanol/CHCl3. In elution volume 850-1400 ml there is recovered 250 mg of the title compound as a white solid: (45.3% yield): 13C-NMR (d6-Acetone) 138.2, 129.2, 128.4, 94.2, 74.5, 73.1, 67.3, 66.7, 65.2, 57.6, 57.5, 55.9, 50.5, 40.3, 32.5, 31.6, 21.2, 20.9 and 14.2 ppm. Exact mass calc'd for C46H78N3O11Si4 (tetra TMS-CHJ: 960.4713; Found: 960.4722. Example 40 3'-(S)-3'-(N-butylaminomethyl)dihydrospectinomycin trihydrochloride Refer to Chart E. In 10 ml of methanol is dissolved 245 mg (0.39 mmol) of N,N'-dibenzyloxycarbonyl-3'-(S)-3'-(N-butylaminomethyl)dihydrospectinomycin (Example 39). To this solution is added 250 mg of Pd black followed by 152 ul of formic acid. The reaction is stirred for 45 min and is filtered. Removal of the solvent in vacuo affords 195.mg of a white solid. The material is taken up in 2 ml of water and 1.5 ml of 1N HCl is added. The solution is frozen and lyophillized to afford 166 mg of a white solid (80; yield): IJC-NHR (D20) 96.2, 95.3, 75.6, 73.4, 70.8, 69.7, 69.5, 65.1, 63.9, 61.7, 54.9, 52.4, 41.7, 34.8, 34.6, 30.8, 23.4, 22.9 and 16.6 ppm. Exact mass calc'd for C37H85N3O7Si6 (Hexas-TMS): 851.5003; Found: 851.4980; Exact mass calc'd for C36H82N3O7Si6 (Hexa-TMS-CH3): 836.4768; Found: 836.4757. Example 41 N,N'-dibenzyloxycarbonyl-3'-(S)-3'-(N-octylamino methyl)dihydrospectinomycin (Formula LXV: Rj and R7 are as in Example 20 and R63 and R64 are as in Example 34) Refer to Chart E. In 5 ml of methanol is dissolved 500 mg (0.79 mmol) of N,N'-dibenzyloxycarbonyl-3 '-(S)-3 '-(aminomethyl )dihydrospectinomycin (Example 31). To this solution is added 1.23 ml of n-octanal and a drop of methyl orange/methanol solution. Then 17 mg of NaCNBH3 in 1 ml of methanol is added. The pH is lowered to 4 with 1N HCl/methanol. The reaction is stirred for 1 hr, maintaining the pH at 4. The methanol is then removed in vacuo and the residue is taken up in CHC13. The solution is washed with 5 ml of brine and dried over MgSO. After filtering, the solvent is removed to afford an oil. The product is taken up in CHCld and chromatographed on 30 g of silica, slurry packed in CHCl. The column is eluted as follows: 200 ml CHCl3; 500 ml 1% methanol/CHCl3; 1 liter 2% methanol/CHCl3; 500 ml 3% methanol/CHCl3; 1 liter 5% methanol/CHCl3. In elution volume 1100-1400 ml there is recovered 186 mg of the title compound as a white solid (32% yield): 1jC-NMR (d6-Acetone) 138.2, 129.2, 128.4, 94.2, 74.5, 74.2, 74.1, 72.9, 67.3, 66.7, 66.5, 65.2, 61.4, 61.1, 60.6, 60.5, 57.6, 57.4, 55.8, 50.8, 40.4, 32.5, 31.5, 30.8, 30.3, 30.1, 29.9, 27.8, 23.2, 21.2, and 14.3 ppm. Exact mass calc'd for C51H89N3O11Si4 (tetra TMS): 1031.5574; Found: 1031.5585. Example 42 3'- (S)-3'- (N-octylaminomethyl )dihydrospectinomycin trihydrochloride Refer to Chart E. In 5 ml of methanol is dissolved 180 mg of N,N'-dibenzyloxycarbonyl-3'-(S)-3'-(N-octylaminomethyl)dihydrospectinomycin. To this solution is added 200 mg of Pd black followed by 94 l of formic acid. The reaction is stirred for 30 min and is filtered. The solvent is removed in vacuo to afford 150 mg of a white solid. The product is taken up in 2 ml of water and 0.8 ml of 1N HCl is added. The solution is frozen and lyophillized overnight to afford 135 mg of a white solid (96 yield): ljC-NMR (D20) 96.2, 95.3, 75.6, 73.4, 70.6, 69.7, 69.5, 65.1, 63.9, 61.7, 54.9, 50.7, 41.8, 34.8, 34.6, 32.0, 29.5, 28.8, 25.8, 23.4, and 17.2 ppm. Exact mass calc'd for C14H93N307Si6 (hexa TMS): 907.5629; Found: 907.5618. Example 43 3'-(R)-3-aminomethyldihydrospectinomycin trihydro chloride (Formula LXII: R3 is methyl) The azide of Example 32, part B, (36 mg, 0.055 mmol) is dissolved in 0.5 ml of methanol and 36 mg of palladium black is added followed by 21 ul (0.55 mmol) of formic acid. The mixture is stirred 10 min at room temperature, and filtered, rinsing the catalyst with four portions of methanol. The filtrate is concentrated in vacuo to afford a colorless material which is dissolved in 5 ml of water and treated with 0.18 ml (0.18 mmol) of 1 N HCl. Lyophillization affords 30 mg of the title product as a white solid. 13C-NMR (D2O, CH3CN internal reference) 6 94.3, 93.6, 73.0, 70.7, 68.4, 67.0, 66.3, 62.6, 60.7, 59.5, 43.4, 40.8, 31.9, 31.6 and 21.1. ExamDle 44 3'-(S)-3'-(n-propylaminomethyl)-31-dihydrospectinomycin trihydrochloride A. In 5 ml of freshly distilled propylamine is dissolved 93 nig (0.151 mmol) of formula LI B-epoxide of Example 32, part A. The resulting solution is refluxed for 2 hr at which time TLC shows complete loss of starting material, with the formation of one more polar, ninhydrin active product. The PrNH2 is removed in vacuo and the residue is stripped down twice from ethyl acetate. The product is then placed on the hi-vacuum pump for 2 hr. This affords 84 mg of a white solid (83% yield). 13C-NMR (d6-Acetone) 138.2, 129.1, 128.3, 94.2, 74.9, 74.4, 74.0, 73.0, 67.2, 66.7, 66.5, 66.3, 65.1, 64.7, 60.3, 57.5, 57.4, 55.8, 52.5, 40.2, 31.5, 23.4, 21.2 and 11.9 6. B. In 5 ml of methanol is dissolved 80 mg (0.12 mmol) of N,N'-dicarbobenzyloxy-3'-(n-propylaminomethyl)dihydrospectinomycin, reaction product of part A. To this solution is added 93 mg of palladium black and 46 ijl of formic acid. The reaction is stirred for 30 min, filtered, and the solvent removed in vacuo to afford 73 mg of a white solid. The product is taken up in 1 ml of water and 4 ml of 0.1 N HCl is added. The sample is frozen and lyophillized to afford 71 mg of a white solid (100X): 13C-NMR (D20) 92.6, 91.7, 71.9, 69.8, 67.0, 66.1, 65.9, 61.5, 60.3, 58.0, 51.4, 50.5, 38.2, 31.2, 19.9, 18.8, and 10.4 6. Exact mass calc'd for C29H64M3O7Si4 (M7-CH3): 678.3821; Found: 678.3791. Example 45 3'-R-3'[(3-dimethylaminopropyl)-aminomelhyl]-diVydro- spectinomycin tetrahydrochloride A. The epoxide (600 mg, 0.98 mmol, Example 32, part A) is dissolved in 5 ml of 3-dimethylaminopropylamine and heated at 60 for 71 hr. The excess is removed in vacuo and the residue is dissolved in 75 ml of EtOAc which is extracted with 2 x 5 ml of H20 and 25 ml of brine, dried with MgSO4 and concentrated to give 600 mg of pale yellow solid. The product is chromatographed on 30 g of 230-400 mesh silica gel packed with 5% MeOH/CHCl, and eluted with 500 ml of 5% MeOH/CHClS with 0.5Z NH,OH, 1 L of 10% MeOH/CHClj with 1% NH4OH and the rest 20% MeOH/CHClj with 1% NH4OH collecting 30 ml fractions. Pooling of fractions 29-56 yields 235 mg (0.33 mmol, 33%) of product as an off white solid: Rf = 0.22 (silica gel, 20 MeOH/CHClq with 1% NH,OH); 13C NMR (CDjCOCD) 6 157, 138.2, 129.1, 128.4, 96.9, 93.8, 74.6, 74.2, 71.8, 67.1, 66.4, 65.2, 60.5, 58.1, 57.6, 54.4, 48.1, 45.4, 44.2, 31.7, 27.3, 21.5; MS exact mass for M+-CHd on tetrakistrimethylsilyl derivative, C47Hb1N40llSi*. Calc'd: 989.4979. Found: 989.4968. MS 1004, 989, 493, 449, 359, 305, 273, 187, 115, 91, 58. B. To a solution of 230 mg (0.32 mmol) of the reaction product of part A in 5 ml of methanol is added 150 mg of palladium black and 0.12 ml (3.2 mmol) of formic acid. The mixture is stirred 3 hr at room temperature and filtered rinsing the catalyst with methanol. The solvent is removed in vacuo and the residue is dissolved in H20 and treated with 1.4 ml (1.4 mmol) of 1N HCl. Lyophilization yields 200 mg (0.33 mol), 100 ) of product as an off white solid: Rf = 0.77 (silica gel, CHCl/MeOH/NH40H, 3/4/2); 13C NMR (D20, CH3CN internal reference) 6 94.1, 93.2, 73.3, 70.5, 68.2, 66.9, 66.2, 62.4, 60.6, 59.3, 55.2, 51.4, 46.4, 43.9, 40.8, 31.9, 31.5, 21.7, 21.0; MS (hexakistrimethylsilyl derivative) 880 (M+), 865, 791, 273, 243, 230, 217, 187, 145, 116, 73, 58; exact mass for M+-CH3, C37H85M4O7Si6. Calc'd: 865.5034. Found, 865.5037. Example 46 N,N '-dicarbobenzyloxy-3'-(R)-3'-(n-butylaminomethyl) 3'-dihydrospectinomycin (Formula LVIII: R62 is n-butyl and R3, R7 and RD1 are as in Example 44) Refer to Chart G. The formula LII a-epoxide of Example 32, part A (40 mg, 0.065 mmol) is dissolved in 2.0 ml of n-butylamine and warmed to 60 with protection from atmospheric moisture for 18 hr. The solvent is removed in vacuo, 5 ml of ethyl acetate is added and the solvent is removed again. The residue is purified by chromatography on a 20 x 20 cm 250 silica gel preparative TLC plate with 254 mm phosphor, eluted with 10% methanol/CHCl. The band with Rf 0.6-0.75 (visualized by short wave UV light) is collected and the product is washed off of the silica gel with ethyl acetate. Concentration in vacuo gives 28 ing (0.040 mmol, 63 ) of title product. 13C-NMR (d6-Acetone) ô 157, 138.2, 129.1, 128.3, 128.1, 97.1, 93.8, 74.6, 74 (broad), 71.7, 67.1, 66.4, 65.2, 61.0, 60.2, 57.6, 54.4, 49.3, 44.5, 32.1, 31.6, 21.5, 20.8, 14.2; Rf = 0.5 (silica gel, 10% methanol/CHCl); MS (for tetratrimethylsilyl derivative) m/z 975, 960, 800, 709, 675, 620, 545, 493, 449, 359, 305, 273, 91. Exact mass for M+ -CH calc'd for C46H78N3O11Si4: 960.4713; Found: 960.4703. Example 47 3-(R)-3'-(n-butylaminomethyl)-3'-dihydrospectinomycin trihydrochloride Refer to Chart D. The Example 46 product is dissolved in 0.5 ml of methanol and 30 mg of palladium black is added followed by 22 wl (0.58 mmol) of 95% formic acid. The mixture is stirred 1 hr at room temperature and filtered, rinsing the catalyst with three portions of methanol. The solvent is removed in vacuo and the residue is dissolved in 4 ml of water. The pH is adjusted to 1.5 with 1N HCl and the solution was lyopholized to afford 21.5 mg of title product as a white solid: 13CNMR (D20, CHCN reference) 6 94.1, 93.3, 73.3, 70.5, 68.3, 66.9, 66.2, 62.5, 60.6, 59.4, 51.0, 49.5, 40.9, 31.9, 31.5, 27.9, 21.0, 20.1, 13.9; Rf = 0.85 (silica gel, CHCl3/methanol/NH4OH, 3:4:2); MS (for tetrakistrimethylsilyl derivative) m/z 707, 692, 621, 349, 273, 171, 158, 145, 86, 73. Exact mass for M+ -CH , calc'd for C,,H,,N,07Si,; 692.3978. Found 692.3967. Example 48 N,N'-dibenzyloxycarbonyl-3'-(S)-spectinomycin cyano hydrin (Formula LXVI I: RR and R1 are as in Example 1) Refer to Chart F. In 25 ml of methanol are combined 5.0 gm (8.33 mmol) of N,N'-di- benzyloxycarbonylspectinomycin and 0.76 ml (8.33 mmol) of acetone cyanohydrin. To this solution is then added 100 mg (0.72 mmol) of K2CO. The reaction is stirred for 4.5 hr and then concentrated in vacuo. The residue is taken up in 40 ml of ethyl acetate, washed once with 50 ml brine and dried over Na2SO,. The solution is then filtered and concentrated in vacuo to afford 5.0 gm of a white solid. The product is taken up in CHCl3 and chromatographed on 200 gm of silica, slurry packed in CHCl. The column is eluted as follows: 1 L 1% methanol/CHCl3; 1 L 2X methanol/CHCl3; 2 L 4% methanol/CHCl3; 2 L 5% methanol/CHCl3. In elution volume 3.3 L to 6.0 L is found 3.92 g of the title compound (75X yield): 13C-NMR (d4-methanol) 138.1, 138.0, 129.4, 129.2, 128.8, 128.4, 94.4, 91.1, 74.8, 74.6, 74.5, 73.3, 68.2, 66.8, 66.4, 66.2, 60.9, 57.8, 42.1, 31.7 and 20.6 ppm; [a] +40 (C, 0.8935, CHCl3). Mass spec m/e 816, 801, 745, 629, 493, 449, 359, 305, 270, 170, 144, 91 and 73. Example 49 3'-(S)-Spectinomycin cyanohydrin diformate Refer to Chart F. In 5 ml of methanol is dissolved 200 mg (0.32 mmol) of N,N-di- carbobenzyloxy-spectinomycin cyanohydrin. To this solution is added 200 mg of Pd black followed by 120 vl (3.2 mmol) of formic acid. The reaction is stirred for 0.5 hr and is filtered. Removal of the solvent in vacuo afforded 170 mg of title product, a white solid: JC-NMR (D,3) 93.5, 91.3, 73.0, 71.3, 68.2, 67.5, 67.4, 67.2, 62.7, 59.6, 41.3, 33.6, 32.0, and 20.6. ExamDle 50 N,N'-dibenzyloxycarbonyl-3'-(S)--3'-(aminomethyl)- dihydrospectinomycin (Formula LXIII: R1 and RX are as in Example 48) Refer to Chart F. In 10 ml of acetic acid is dissolved 3.33 g (5.31 mmol) of N,N' dibenzyloxycarbonylspectinomycin-3'-(S)-cyanohydrin, Example 48. The solution is added to a Paar bottle containing 5.0 g of wet Raney nickel. Tie solution is then hydrogenated for 3.5 hr at an initial pressure of 15 psi. The solution is then filtered through magnesium silicate and the acetic acid is removed in vacuo. The residue is partitioned between water and ethyl acetate. The water is separated and combined with 2, 100 ml 1N HCl washes of the ethyl acetate. The aqueous washes are made alkaline with 1N NaOH (pH=10) and extracted with ethyl acetate (2 x 100 ml). The combined organic extracts are then washed with 100 ml of brine and are dried over MgSO4. After filtering, removal of the solvent in vacuo leaves 1.323 g (406 yield) of the title compound: 13C-NMR (d4-methanol) 158.9, 158.4, 138.1, 129.5, 129.0, i28.7, 94.8, 93.7, 74.7, 73.9, 73.3, 68.7, 68.3, 67.7, 56.8, 65.7, 61.2, 57.9, 45.8, 39.7, 31.8 and 21.2 ppm. Example 51 N,N '-dibenzyloxycarbonyl-3'- (R)-spectinomycin cyano hydrin (Formula LXVIII: R1 and R3 are as in Example 48) Refer to Chart F. In 1 ml of methanol are combined 1.0 g (1.66 mmol) of N,N'-dibenzyloxycarbonylspectinomycin and 0.152 ml (1.66 mmol) of acetone cyanohydrin. To this solution is added 0.5 g of Amberlite IR-45 C.P. resin, followed by 1 ml of saturated aqueous NH4Cl. The reaction is stirred for 24 hr at room temperature. The reaction is then filtered and the methanol removed in vacuo. the residue is partitioned between ethyl acetate and water. The ethyl acetate is separated and combined with the, ethyl acetate extract of the aqueous phase. The combined extracts are washed with brine and dried over MgSO4. After filtering, the solvent is removed in vacuo to afford 1.229 g of a white solid. The material is taken up in CHCl and chromatographed on 35 g of silica, slurry packed in CHCl. The column is eluted as follows: 200 ml 1% methanol/CHCl3; 1 L 2% methanol/CHCl3 and 1 L 4% methanol/CHCl3. Elution volume 600-850 ml contains 364 mg of N,N'-dibenzyloxycarbonylspectinomycin. Elution volume 1100-1200 ml contains 131 mg of the title compound while 207 mg of N,N'-dibenzyloxycarbonyl-3'-(S)- spectinomycin cyanohydrin is found in elution volume 1450 ml-2100 ml. The yield of the desired cyanohydrin is 20%: 13C-NMR (dt-Acetone) 156.9, 137.8, 129.0, 128.3, 120.1, 95.2, 91.5, 73.3, 74.8, 74.5, 74.1, 73.9, 67.8, 67.3, 66.2, 60.7, 60.6, 60.4, 57.6, 57.5, 57.3, 42.0, 31.7 and 20.6 ppm. Example 52 N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(aminomethyl)- dihydrospectinomycin (Formula LXIV: R1 and Rj are as in Example 48) Refer to Chart F. In 1 ml of acetic acid is dissolved 130 mg (0.21 mmol) of N,N' dibenzyloxycarbonyl-3'-(R)-spectinomycin cyanohydrin (Example 51). This solution is added to a Paar bottle containing 0.5 gm of wet Raney-Nickel. The solution is hydrogenated at 15 psi for 2 hr. The solution is filtered through magnesium silicate and rinsed with methanol. The filtrate is concentrated in vacuo and the residue partitioned between diethyl ether and water. The aqueous phase is separated and made alkaline with the addition of concentrated NH40H (pH-9). The basic solution is extracted with ethyl acetate (2 x 20 ml). The combined extracts are washed with 20 ml of brine and dried over MgSO4. After filtering, removal of the solvent leaves 73 mg of the title compound (56.65 yield). Example 53 N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(aminomethyl) dihydrospectinomycin (Formula LXIV: R1 and Rj are as in Example 48) In 25 ml of methanol is dissolved 10.0 g (16.6 mmol) N,N'-dicarbobenzyloxy-spectinomycin and 7.6 ml (83.2 mmol) of acetone cyanohydrin. To this solution is added 5.0 g of IR-45 C.P. resin. The mixture is stirred for 3.5 hr, filtered and concentrated in vacuo. The residue is taken up in ethyl acetate and washed with water (2 x 50 ml). The combined washes are backwashed with ethyl acetate (1 x 20 ml). The combined organics are washed with 50 ml of brine and dried over MgSO4. After filtering, removal of the solvent in vacuo affords 11.34 g of a white solid. By TLC the products consist of unreacted material and both formula LXVII and LXVII I cyanohydrin epimers. The mixture is dissolved in 50 ml of acetic acid and the solution is added to a Paar bottle containing 17 g of wet Raney-Nickel. The solution is hydrogenated at 15 psi for 1 hr, and filtered through Magensol. The filtrate is concentrated in vacuo and the residue partitioned between diethyl ether and water. Enough ethyl acetate is added to solublize everything. The aqueous phase is separated and made alkaline with concentrated NH4OH. The basic solution is extracted with ethyl acetate. An emulsion forms which is broken up by filtering through diatomaceous earth. The ethyl acetate is separated and combined with a 100 ml ethyl acetate extract of the aqueous phase. The combined extracts are washed with brine, dried over MgSOW and filtered. Removal of the solvent affords 3.49 g of a blue solid. The product is taken up in CHClj and chromatographed on 100 g of silica, slurry pacKed in CHCl. The column is eluted as follows, with 1% aqueous NH40H added to the mobile phase: 200 ml 1X methanol/CHCl; 200 ml 2% methanol/CHCl; 200 51 3 methanol/CHCl3; 200 ml 42 methanol/CHCl; 3 L 5% methanol/CHCl; 1 L 10% methanol/CHCl3. In elution volume 2.5 l to 4.2 l there is obtained 1.173 g of the title compound as a white solid (11.2t yield, based on starting material: 13C-NMR (d4-methanol) 158.23, 138.0, 129.4, 128.8, 128.6, 96.3, 94.3, 74.6, 73.8, 68.1, 66.7, 65.5, 60.9, 60.8, 58.0, 45.6, 41.4, 31.8 and 21.5 ppm. Example 54 N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N-hexylamino methyl)-dihydrospectinomycin (Formula LXVI: R63 is hydrogen and Rb4 is n-hexyl, R1 and R3 are as in Example 48) and N,N'-dicarbobenzyloxy-3'-(N,N- dihexylamino-methyl )-dihydrospectinomycin (Formula LXVII: R63 and R64 are both n-hexyl). In 10 ml of methanol are combined 500 mg (0.79 mmol) of N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(aminomethyl)-dihydrospectinomycin, 0.95 ml (7.9 mmol) of n-hexanal and 16.5 mg (0.26 mmol) of NaCNBH. A trace of methyl orange indicator is added and the pH is adjusted to the indicator's end point using 1N HCl/methanol. The reaction is stirred for 2 hr at room temperature, during which time an additional 33 mg (0.52 mmol) of NaCNBHb is added. The solvent is then removed in vacuo and the residue partitioned between water and ethyl acetate. The ethyl acetate is separated and combined with a 20 ml ethyl acetate extract of the aqueous phase. The combined extracts are washed with 50 ml of brine and dried over MgSO. After filtering, removal of the solvent affords an oil which is immediately taken up in CHCl3 and chromatographed on 35 g of silica, slurry packed in CHClt. The column is eluted as follows: 100 ml CHCl 3; 200 ml 1% methanol/CHCl; 200 ml 21 methanol/CHCl; ; 200 ml 3% methanol/CHCl; and 1 liter of 5% methanol/CHCl3. In elution volume 400-900 ml there is obtained 310 mg (49% yield) of N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N,N-dihexylamino- methyl)-dihydrospectinomycin as a white solid: 13C-NMR (d6-Acetone) 138.2, 129.1, 128.7, 128.4, 128.2, 97.2, 93.8, 74.7, 74.4, 72.2, 67.2, 66.5, 65.4, 65,2, 61.0, 60.4, 60.3, 59.7, 57.7, 57.5, 55.9, 44.6, 32.4, 32.2, 32.0, 31.8, 31.5, 27.6, 26.9, 23.2, 21.5 and 14.3 ppm. Exact mass calc'd for C54H94N3O11Si4 (tetra TMS-CH): 1072.5965; Found: 1072.5968. Elution volume 950-1400 ml contains 109 mg (19.3%) of N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N-hexylaminomethyl)-dihydrospectinomycin as a white solid: 13C-NMR (db-Acetone) 138.1, 129.1, 128.3, 128.1, 97.0, 93.8, 74.5, 71.7, 67.2, 66.4, 65.2, 57.6, 54.3, 49.7, 44.4, 32.2, 31.6, 29.9, 27.4, 23.1, 21.5, and 14.2 ppm. Exact mass calc'd for C49H85N3O11Si4 (tetra TMS): 1003.5261; Found: 1003.5278. Example 55 N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N-isobutylamino methyl)-dihydrospectinomycin and 3'-(N,N-diisobutyl aminomethyl)-dihydrospectinomycin (Formula LXVI: R63 is hydrogen or isobutyl, respectively, R64 is isobutyl, and R1 and Rd are as in Example 48) Refer to Chart F. To a solution of 500 mg (0.79 mmol) of N,N'-dibenzyloxycarbonyl- 3'-(R)-3'-(aminomethyl)-dihydrospectinomycin in 10 ml of methyl alcohol is added 0.72 ml (7.9 mmol) of isobutyraldehyde and a trace of methyl orange indicator. The pH is adjusted to the indicator's end point with methanolic HCl and 16.5 mg (0.26 mmol) of sodium cyanoborohydride in 1 ml of methyl alcohol is added. The reaction is stirred at room temperture and the pH is maintained near the endpoint of methyl orange by adding additional methanolic HCl. The reaction is easily followed by TLC using Analtech Silica plates and eluting with 10% MeOH/CHClj NH OH as a solvent. When the reaction is complete, the solvent is removed in vacuo and the residue is partitioned between HzO and EtOAc. The aqueous phase is made alkaline with the addition of concentrated NH.40H and the EtOAc is separated and combined with an additional EtOAc extract. The combined extracts are washed with brine and dried over MgSO4. The solvent is then removed in vacuo to afford the crude product. The product is taken up in CHClj 9 and chromatographed on silica, slurry packed in CHCl. The column is eluted with a MeQH/CHClj gradient (1%-5%), and 50 ml fractions are taken. The fractions are analyzed by TLC and pure fractions are pooled and concentrated in vacuo to afford 216 mg (39.8%) of N,N'dibenzyloxycarbonyl-3'-(R)-3'-(N-isobutylaminomethyl)dihydrospectinomycin: 19C NMR (d6-acetone): 138.1, 129.1, 128.6, 128.3, 128.1, 97.1, 93.8, 74.5, 71.7, 67.2, 66.4, 65.2, 57.8, 54.6, 44.4, 31.8, 31.6, 28.4, 21.5, 20.9, ana 20.8 ppm. Eact mass calc'd for C47H81N3O11i4 (tetra TMS) 975.4948, found 975.4943. The same procedure, using 631 mg (1.0 mmol) of the amine, 1.82 ml (20 mmol) of aldehyde and 188 mg (3.0 mmol) of sodium cyanoborohydride afforded 171 mg (23%) of N,N-dibenzyloxycarbonyl-3'-(R)-3'-(N,N- diisobutylaminomethyl)-dihydrospctinomycin: 13C NMR (d-acetone) 138.1, 129.1, 128.3, 128.1, 97.0, 93.5, 74.6, 73.1, 67.3, 67.2, 66.4, 65.2, 61.1, 57.5, 44.1, 31.4, 26.8, 21.7 and 21,4 ppm; exact mass calc'd for C48H81N3O11Si4 (tri-TMS) 959.5179, found, 959.5134. Example 56 N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N-cyclohexylmethyl- aminomethyl)-dihydrospectinomycin and N,N'-dibenzyloxy carbonyl-3 ' (R)-3 '-[N,N-di (cyclohexylmethyl )amino methyll-dihydrospectinomycin (Formula LXVI: R63 is hydrogen or cyclohexylmethyl, respectively, R64 is cyclohexylmethyl, and R1 and R 3 are as in Example 48.) Alkylation of 2.4 9 (3.9 mmol) of N,N'-dibenzyloxycarbonyl-3' (R)-3'-(aminomethyl)dihydrospectinomycin using 2.11 ml (19.5 mmol) of cyclohexane carboxaldehyde and 180 mg (2.8 mmol) of sodium cyanoborohydride following the procedure in example 55 afforded 982 mg (31%) of N,N'-dibenzyloxycarbonyl-3'-(R)-3'-[(N-cyclohexylmethyl)-aminomethyl]dihydrospectinomycin: : 1JC-NMR (d6-Acetone) 138.1, 129.1, 128.3, 97.0, 93.7, 74.5, 71.7, 67.2, 66.5, 65.2, 57.6, 56.5, 54.6, 44.5, 38.0, 31.9, 31.6, 27.2, 26.5, and 21.5 ppm; exact mass calc'd for C50Hb5NjOllSi4 (tetra TMS) 1015.5261, found 1015.5240. Alkylation of 634 mg (1.0 mmol) of the amine using 1.08 ml (10 trimol) of aldehyde and 62.8 mg (1.0 mmol) of sodium cyanoborohydride gave 173 mg (21%) of N,N'-dibenzyloxycarbonyl-3'-(R)-3'-5N,N-di(cyclo- hexylmethyl)-aminomethyl]-dihydrospectinomycin: 19C-NMR (d6-Acetone) 129.1, 128.4, 128.2, 97.3, 93.5, 74.7, 72.9, 67.4, 67.2, 66.5, 65.1, 61.2, 57.7, 57.6, 57.4, 44.6, 36.5, 32.6, 32.4, 31.7, 27.2, 26.7 and 21.4 ppm; exact mass calc'd for C5jHdbN3O115J (tri TMS-CH) 1024.5570, found 1024.5526. Example 57 Deprotection of the N,N'-dibenzyloxycarbonyl-3'-(R)-3'- mono and di-alkylaminomethyl-dihydrospectinomycin of Examples 54-56: The protected products of Example 54, 55, or 56 is dissolved in methanol and an equivalent weight of Pd black is added. To this mixture is added 20 equivalents of formic acid. The reaction is stirred for 45 min, filtered and concentrated to dryness. The residue is taken up in water and 3.5 equivalents of 1N HCl are added. The solution is frozen and lyophillized to afford the following final products: (a) 3'-(R)-3'-(N-hexylaminomethyl)-dihydrospectinomycin trihydrochloride: Deprotection of 87 mg (0.12 mmol) affords 58 mg (87% yield) of the title compound as a white solid: 13C-NMR (D20) 94.1, 93.3, 73.2, 70.5, 68.3, 66.9, 66.2, 62.5, 60.6, 59.3, 51.0, 49.8, 40.9, 31.9, 31.5, 31.4, 26.3, 25.8, 22.7, 21.0 and 14.3 ppm. Exact mass calc'd for C39H89N8O7Si6 (hexa-TMS): 879.5316; Found: 879.5303. (b) 3'-(R)-3'-(N-isobutylaminomethyl)-dihydrospectinomycin trihydrochloride: Deprotection of 216 mg (0.29 mmol) affords 152 mg (90% yield) of the title compound as a white solid: 13C-NMR (D2O) 93.9, 93.3, 73.0, 70.3, 68.1, 66.8, 66.1, 62.3, 60.5, 59.2, 56.3, 51.3, 41.2, 31.8, 31.4, 25.5, 21.0, 19.9, and 19.7 ppm; exact mass calc'd for C37H85N3O7Si6 (hexa TMS) 851.5003, found 851.5020. (c) 3'-(R)-3'-(N-cyclohexylmethylaminomethyl )-dihydrospectino mycin trihydrochloride: Deprotection of 928 mg (1.12 mmol) afford 640 mg of the title compound as a white solid (86 yield): 13C-NMR (D > O) 94.2, 93.5, 73.2, 70.6, 68.3, 66.9, 66.3, 62.5, 60.6, 59.4, 55.3, 51.5, 41.3, 34.6, 31.9, 31.5, 30.7, 26.5, 25.9, and 21.0 ppm; exact mass calc'd for C40H89N3O7Si6 (hexa TMS) 891.5316, found 891.5324. (d) 3 r¯ (R)-3'-(N,N-dihexylaminomethyl)-dihydrospectinomycin trihydrochloride: Deprotection of 220 mg (0.28 mmol) affords 157 mg (88; yield) of the title compound as a white solid: 13C-NMR (020) 94.1, 93.3, 70.5, 68.3, 68.1, 66.7, 66.6, 66.5, 66.3, 62.4, 60.5, 59.3, 56.9, 56.7, 31.9, 31.5, 26.3, 23.7, 22.8, 21.0 and 14.4 ppm. Exact mass calcd for C24H93N3O7Si6 (hexa TMS): 891.5860; found: 891.5853. (e) 3'-(R)-3'-(N,N-diisobutylaminomethyl)-dihydrospectinomycin tri hydrochloride: Deprotection of 153 mg (0.20 mmol) affords 96 mg of the title compound (82% yield): 13C-NMR (D20) 94.3, 93.9, 73.3, 70.6, 68.2, 66.7, 66.6, 65.7, 62.6, 60.7, 59.6, 43.3, 31.9, 31.8, 31.6, 25.1, 24.8, 21.1, 21.0, 20.6, 20.4, 19.8 and 19.6 ppm; exact mass calc'd for C38H85N3O7Si5 (penta-TMS) 835.5234, found 835.5241. (f) 3'-(R)-3'-(N,N-di[cyclohexylmethyl]aminomethyl)dihydro- spectinomycin trihydrochloride: Deprotection of 149 mg (0.18 mmol) affords 124 mg of the title compound as a white solid (100 yield): 13C-NMR (duo) 94.3, 93.8, 73.2, 70.5, 68.2, 66.9, 66.5, 65.2, 64.5, 62.6, 60.7, 59.5, 43.2, 34.1, 33.7, 31.9, 31.8, 31.3, 30.9, 30.7, 26.5, 25.9, and 21.1 ppm; exact mass calc'd for C41H85N3O7Si4 (tetra TMS) 843.5465, found 843.5459. Example 58 N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(cycloalkylamino- methyldihydrospectinomycins (Formula XLVI: At least one of R63 and Rb4 is cycloalkyl.) Refer to Chart F. In 3 ml of methanol are combined 1 mmol of N,N'-dibenzyloxycar bonyl-3'-(R)-3'-(aminomethyl)dihydrospectinomycin, Example 52, and 10 mmol of the cycloalkanone. To this solution is added 0.33 mmol of sodium cyanoborohydride. The pH is adjusted to 6 with methanolic hydrogen chloride. The reaction is followed by TLC on silica eluting with 90:10:1 chloroform/methanolZconcentrated aqueous ammonia. When the reaction is complete, the solvent is removed in vacuo and the residue partitioned between ethyl acetate and water, made alkaline with concentrated aqueous ammonia. The ethyl acetate is separated, combined with a second extract, washed with brine and dried over magnesium sulfate. After filtering, the solvent is removed in vacuo and the residue chromatographed on 40 g of silica, slurry packed in chloroform. The column is eluted with a methanol chloroform gradient and 45 ml fractions are collected. The desired product is found by TLC analysis. The pure fractions are pooled and concentrated to afford the following final products: (a) N,N'-dibenzylOxycarbonyl-3'-(R)-3'-(cyclopentylaminomethyl)- dihydrospectinomycin (Formula LXVI: R63 is cyclopentyl and R64 is hydrogen.) The title compound is obtained in a 47% yield, 328 mg of a white solid were obtained: 13C-NMR (d6-acetone) 157.0, 138.2, 129.1, 128.3, 128.1, 97.2, 93.8, 74.6, 71.7, 67.1, 66.0, 65.2, 60.9, 60.2, 59.6, 57.7, 57.6, 57.5, 53.0, 44.6, 33.3, 32.5, 31.6, 24.4, 24.3, and 21.5 ppm; exact mass calc'd for C48H81N3O11Si4 (tetra TMS) 987.4948. Found 987.4924. (b) N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(cyclohexylaminomethyl )dihydrospectinomycin (Formula LXVI: R63 is cyclohexyl and R64 is hydrogen.) Chromatography affords 240 mg (34% yield) of the title compound as a white solid: 13C-NMR (db-acetone) 157.0, 138.2, 129.1, 128.3, 128.1, 97.2, 93.8, 74.6, 71.6, 67.1, 67.0, 66.4, 65.2, 60.9, 60.2, 57.6, 57.5, 56.6, 51.4, 44.5, 33.4, 33.3, 31.6, 26.6, 25.4, and 21.5 ppm; exact mass calc'd for C4sH-1NjOllSi4 (tetra TMS): 1001.5104. Found: 1001.5132. (c) N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(cycloheptylaminomethyl)- dihydrospectinomycin (Formula LXVI: R63 is cycloheptyl and R64 is hydrogen.) Chromatography affords 178 mg (24.5%) of the title compound as a white solid: 13C-NMR (d-acetone) 157.0, 138.0, 129.0, 128.2, 128.0, 97.0, 93.6, 74.5, 71.5, 67.1, 66.4, 65.2, 60.6, 60.0, 58.7, 57.5, 51.7, 44.5, 34.7, 34.6, 31.6, 28.8, 24.5, and 21.4 ppm; exact mass calc'd for C50H85N3O11Si4: 1015.5261. Found: 1015.5282. Example 59 Preparation of 3'-(R)-3'-(cycloalkylaminomethyl) dihydrospectinomycin trihydrochlorides Refer to Chart F. The N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(cycloalkylaminomethyl)- dihydrospectinomycin (Example 58) and an equal weight of palladium black are combined in 10 ml of methanol. To the mixture is added 10 equivalents of formic acid. After stirring for 20 min, the reaction mixture is filtered and the solvent is removed in vacuo. The solid residue is taken up in water and treated with 3.5 equivalents of 1N hydrochloric acid. The solution is frozen and lyophilized to afford the following final products: (a) 3 '-(R)-3'-(cyclopentylaminomethyl )dihydrospectinomycin trihydrochloride Deprotection of 320 mg (0.45 mmol) affords 244 mg (100%) of the title compound as a white solid: 13C-NMR (duo) 94.2, 93.3, 73.4, 70.6, 68.4, 67.0, 66.3, 62.6, 61.8, 60.7, 59.4, 50.4, 40.7, 31.9, 31.5, 30.1, 24.7, and 21.0 ppm; exact mass calc'd for C39H87N3O7Si6 (hexa-TMS): 877.5159. Found: 877.5143. (b) 3'-(R)-3'-(cyclohexylaminomethyl)dihydrospectinomycin trihydrochloride Deprotection of 240 mg (0.33 mmol) affords 154 mg (84.1% yield) of the title compound as a white solid: 1dC-NMR (D20) 94.1, 93.3, 73.3, 70.6, 68.3, 66.9, 66.3, 62.5, 60.6, 59.8, 59.4, 48.1, 40.8, 31.9, 31.5, 29.5, 29.3, 25.4, 25.0, and 21.0 ppm. Exact mass calc'd for C39H87N3O7i6 (hexa TMS): 877.5159. Found 877.5143. (c) 3'- (R)-3'-(cycloheptylaminomethyl )dihydrospectinomycin trihydrochloride Deprotection of 160 mg (0.22 mmol) affords 120 mg (96g) of the title compound as a white solid: 13C-NMR (D20) 94.1, 93.3, 73.3, 70.5, 68.3, 66.9, 66.3, 62.5, 61.7, 60.6, 59.3, 48.1, 40.9, 31.9, 31.5, 31.1, 27.9, 24.6, and 21.0 ppm; exact mass calc'd for C40H89N3O7Si6 (hexa IMS): 891.5316. Found: 891.5350. Example 60 N,N'-dibenzyloxycarbonyl-3'-(R)-3'-[(2-hydroxyethyl) aminomethyl]dihydrospectinomycin (Formula LXVI: R63 is hydrogen and R64 is 2-hydroxyethyl.) Refer to Chart F. In 5 ml of methanol are combined 1.0 g (1.6 mmol) of N,N'dibenzyloxycarbonyl-3'-(R)-3'-(aminomethyl)dihydrospectinomycin (Example 52) and 528 mg (8.8 mmol) of glycolaldehyde. The pH is adjusted to 4 with IN methanolic hydrogen chloride and 33 mg of sodium cyanoborohydride in 1 ml of methanol is added. The reaction is stirred for 30 min and the solvent is removed in vacuo. The residue is partitioned between ethyl acetate and water, made alkaline with concentrated aqueous ammonia. The ethyl acetate is separated and combined with an additional ethyl acetate extract. The extracts are then washed with brine and dried over magnesium sulfate. After filtering, the solvent is removed in vacuo to afford 966 mg of a white solid. The product is taken up in chloroform and chromatographed on 35 9 of silica, slurry packed in chloroform. The column is then eluted with 1% methanol chloroform (200 ml), 2% (200 ml), 5t (200 ml) and 10% (1 1). Elution volumne 900-1050 ml contains 311 mg of the title compound (39% yield): 1jC-NMR (d6-acetone) 157.7, 138.2, 129.1, 128.4, 128.2, 97.0, 93.9, 74.6, 71.8, 67.2, 66.4, 65.2, 61.2, 60.9, 60.3, 57.7, 57.6, 54.2, 51.8, 44.4, 31.7, and 21.5 ppm; exact mass calc'd for C4tlH85N3012Si5: 1035.4979. Found: 1035.4965. Example 61 N,N'-dibenzyloxycarbonyl-3'-(R)-3'-[(5-hydroxylpentyl)- aminomethylzdihydrospectinomycin (Formula LXVI: R63 is hydrogen and R64 is 5-hydroxypentyl.) Refer to Chart F. In 95 ml of methanol are combined 5.0 g (7.9 mmol) of N,N' dibenzyloxyCarbonyl-3'-(R)-3'-(aminomethyl)dihydrospectinomycin (Example 52) and 7.6 ml (8.02 g, 79 mmol) of 5-hydroxypentanal. The pH is adjusted to 4.5-5.0 with 2N HCl in methanol and 51.1 mg (0.813 mmol) of sodium cyanoborohydride is added. The reaction is allowed to stir for 40 min and the solvent is removed in vacuo. The residue is partitioned between water and ethyl acetate. The aqueous phase is made alkaline with concentrated aqueous ammonia and the ethyl acetate is separated. The extract is combined with an additional ethyl acetate extract of the aqueous phase. The extracts are then washed with brine and dried over magnesium sulfate. After filtering, the solvent is removed in vacuo to afford 9.31 9 of a liquid. The product is taken up in chloroform and chromatographed on 300 g of silica, which is slurry packed in chloroform. The column is eluted with 1% methanol chloroform (1 1), 2t (1 1), 3% (2 1), 4% (2 1), 5% (2 1), 5% with 0.5% added concentrated aqueous ammonia (4 1) and 10% with 1X added concentrated ammonia (2 1). The desired product is found by TLC analysis of each 50 ml fraction. The pure fractions are combined and the solvent removed to afford 1.82 g (32% yield) of the title compound as a white solid: 13C-NMR (d6-acetone) 138.2, 129.1, 128.4, 128.2, 97.1, 93.6, 74.6, 71.7, 67.2, 66.5, 65.3, 62.3, 57.6, 54.4, 49.7, 44.5, 33.3, 31.7, 29.8, 24.2 and 21.6 ppm; exact mass calc'd for C5lHs1N 012Sib (penta IMS): 1077.5449. Found: 1077.5492. Example 62 N,N'-dibenzyloxycarbonyl-3l-(R)-3'-[(6-chloroheXyl)- aminomethyl]dihydrospectinomycin (Formula LXVI: R6z is hydrogen and Rb4 is 6-chlorohexyl). Refer to Chart F. In 20 ml of methanol are combined 1.0 g (1.58 mmol) of N,N' dibenzylOxyCarbonyl-3'-(R)-3'-(aminomethyl)dihydrospectinomycin (Example 52) and 1.08 g (8.06 mmol) of 6-chlorohexanal. To this solution is added 33 mg (0.52 mmol) of sodium cyanoborohydride. The pH is adjusted to 4 with 2N methanolic hydrogen chloride and the reaction is allowed to stir for 30 min. The solvent is removed in vacuo and the residue partitioned between ethyl acetate and water, made alkaline with concentrated aqueous ammonia. The ethyl acetate was separated and combined with a second ethyl acetate extract. The combined extracts are washed with saturated aqueous sodium bisulfite and brine. After drying over magnesium sulfate, the solvent is removed in vacuo to afford 1.371 g of a white solid. The product is taken up in chloroform and chromatographed on 100 g of silica, slurry pacKet in chloroform. The column is eluted witn 500 ml of chloroform, 1% methanol chloroform (1 L) 2; (1 t) and 5% (1 ±). The desired product is found by TLC analysis of each 45 ml fraction. Fractions 50-60 are pooled and concentrated to afford 170 mg (14% yield) of the title compound as a white solid: 13C-NMR (d6-acetone) 157.5, 156.6, 138.2, 129.1, 128.3, 128.1, 97.1, 93.8, 74.6, 71.7, 67.2, 66.4, 65.2, 61.0, 57.7, 57.6, 54.3, 49.6, 45.6, 44.5, 33.2, 31.6, 29.8, 27.2, 27.0, and 21.5 ppm: Exact mass calcd for C4eH8lClNdO1lSi4 (tetra TMS minus methyl): 1022.4636. Found: 1022.4607. Example 63 N,N'-dicarbobenzyloxy-3'-(R)-3'-[carbomethoxymethyl)- aminomethyludihydrospectinomycin (Formula LXVI: R is hydrogen and R64 is carbomethoxymethyl). Refer to Chart F. In 5 ml of methylene chloride are combined 1.13 g (1.8 mmol) of N,N '-dibenzyl oxycarbonyl-3 '-(R)-3 '-(aminomethyl )dihydrospectinomycin (Example 52) and 1.58 mg (1.8 mmol) of methyl glyoxylate. The resulting solution is refluxed for 5 hr and the solvent removed in vacuo. The solid residue is taken up in methanol and treated with 4.52 mg (7.2 mmol) of sodium cyanoborohydride. The pH is adjusted to 4 with 2N methanolic hydrogen chloride and the reaction is stirred for 30 min. The solvent is removed in vacuo and the residue partitioned between ethyl acetate and water, made alkaline with concentrated aqueous ammonia. The ethyl acetate is separated and combined with a second ethyl acetate extract. The extracts are washed with brine and dried over magnesium sulfate. After filtering, the solvent is removed in vacuo to afford 1.12 g of a white solid. The product is taken up in chloroform and chromatographed on 40 g of silica, slurry packed in chloroform. The column is eluted with 1% methanol chloroform (500 ml), 2% (1 ±) and 3% (1 Q). Each 45 ml fraction is analyzed by TLC. Fractions 15-28 are pooled and concentrated to afford 697 mg (55.1%) of the title compound as a white solid: 13C-NMR (d6-acetone) 172.5, 156.0, 138.1, 129.1, 128.3, 128.1, 96.6, 93.7, 74.4, 72.1, 67.1, 66.4, 65.2, 60.0, 57.6, 53.4, 51.9, 50.3, 31.6, and 21.5 ppm; Exact mass calcd for Cq5H77N301sSi4 (tetra TMS): 991.4534. Found: 991.4499. Example 64 3'-(R)-3'-E(2-hydroxyethyl)aminomethyl]dihydrospectino- mycin trihydrochloride Refer to Chart F. In 5 ml of methanol is dissolved 300 mg (0.44 mmol) of N,N' dibenzyloxcarbonyl-3'-(R)-3'-[(2-hydroxyethyl)aminomethyl]dihydro- spectinomycin (Example 60). To this solution is added 300 mg of palladium black followed by 173 ul (4.4 mmol) of formic acid. The reaction is stirred for 20 min, filtered and concentrated in vacuo to afford 215 mg of a white solid. The product is taken up in water and treated with 1.5 ml of 1N hydrochloric acid. The solution is frozen and lyophlized to afford 200 mg of the title compound as a white solid (88.1% yield): 13C-NMR (D20) 94.1, 93.4, 73.1, 70.5, 68.3, 66.9, 66.3, 62.5, 60.6, 59.4, 57.0, 51.3, 50.8, 41.3, 31.9, 31.6, and 21.0 ppm; Exact mass calcd for CHbgNs08Si7 (hepta TMS): 911.5034. Found 911.4995. Example 65 3'-(R)-3'-[(5-hydroxypentyl)aminomethyl]dihydrospectin- omycin trihydrochloride Refer to Chart F. In 10 ml of methanol are combined 720 mg (1.0 mmol) of N,N'dibenzyloxycarbonyl-3'-(R)-3'-[(5-hydroxypentyl)aminomethyl]dihydrospectinomycin (Example 61) and 320 mg of palladium black. To this solution is added 390 vl (10.0 mmol) of formic acid. The mixture is stirred for 30 min, filtered and concentrated in vacuo to afford 584 mg of a white solid. The product is taken up in water and treated with 4 ml of 1N hydrochloric acid. The solution is frozen and lyophilized to afford 539 mg (96.8%) of the title compound as a white solid: 13C-NMR (duo) 93.9, 93.3, 73.1, 70.3, 68.2, 66.7, 66.1, 62.3, 62.1, 604, 59.2, 50.9, 49.5, 40.7, 31.8, 31.5, 25.5, 23.0 and 20.9; Exact mass calcd for C4lHy5NjObSi7 (hepta TMS): 953.5504. Found: 953. 5555. Example 66 3'-(R)-3'-[(6-chlorohexyl)aminomethyl]dihydrospctino mycin trihydrochloride Refer to Chart F. In 5 ml of methanol is dissolved 138 mg (0.18 mmol) of N,N'dibenzyloxycarbonyl-3'-(R)-3'-[(6-chlorohexyl)aminomethyl]dihydro spectinomycin (Example 62). To this solution is added 116 mg of palladium black followed by 70 pl (1.8 mmol) of formic acid. The reaction is stirred for 5 min and is filtered. Removal of the solvent in vacuo affords a white solid which is taken up in water and treated with 1 91 of 1N hyerochloric acid. The solution is frozen and lyophilized to afford 94 mg (88.3 yield) of the title compound as a white solid: 13C-NMR (DzO) 94.2, 93.4, 73.4, 70.7, 68.4, 67.0, 66.4, 62.6, 60.7, 59.5, 51.1, 49.7, 46.7, 41.0, 32.6, 31.9, 31.6, 26.6, 26.0, 25.8 and 21.0 ppm; Exact mass calcd for C49H72N3O7Si6 (hexa TMS): 913.4926. Found: 913.4930. Example 67 3'-(R)-3'-[(carbomethoxymethyl)aminomethyl]dihydro spectinomycin trihydrochloride. Refer to Chart F. In 5 ml of methanol is dissolved 200 mg (0.28 mmol) of N,N'dibenzyloxycarbonyl-3'-(R)-3'-[(carbomethoxymethyl)aminomethyl]dihydrospectinomycin (Example 63). To this solution is added 200 mg of palladium black and 0.122 ml (3.12 mmol) of formic acid. The reaction is stirred for 20 min, filtered, and concentrated in vacuo to afford 127 mg of a white solid. The product is taken up in water and treated with 1 ml of 1N hydrochloric acid. The solution is frozen and lyophilized to afford 133 mg (87% yield) of the title compound as a white solid: 13C-NMR (D2O) 168.4, 94.0, 93.3, 73.1, 70.4, 68.2, 66.8, 66.2, 62.4, 60.5, 59.3, 54.5, 51.8, 48.9, 41.1, 31.8, 31.5, and 21.0 ppm; Exact mass calcd for C30H65N3O9Si4 (tetra TMS): 723.3798. Found: 723.3823. Example 68 N,N'-dibenzyloxycarbonyl-3'-(R)-3'-5(benzyloxyCarbonyl- methyl)aminomethyl] dihydrospectinomycin (Formula LXVI: R63 is hydrogen and R64 is benzyloxycarbonyl methyl) Refer to Chart F. In 10 ml of ethylene dichloride are combined 631 mg (1 mmol) of N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(aminomethyl)dihydrospctinomycin, and 164 mg (1 mmol) of benzylglyoxylate. The solution is refluxed for 3 hr and the solvent is removed in vacuo. The yellow solid obtained is taken up methanol and treated with 105 mg of sodium cyanoborohydride (1.67 mmol), added portionwise over a period of 2 hr. The pH is maintained at 4 by adding 2N methanolic hydrogen chloride. The solvent is removed in vacuo and the residue partitioned between ethyl acetate and water, made alkaline with concentrated aqueous ammonia. The ethyl acetate is separated and combined with a second ethyl acetate extract. The extracts are washed with brine and dried over magnesium sulfate. After filtering, the solvent is removed in vacuo to afford 771 mg of a white solid. The product is taken up in chloroform and chromatographed on 37 g of silica, slurry packed in chloroform. The column is eluted with 1% methanol/chloroform (500 ml), 2% (1 1) and 3% (1 1), and 45 ml fractions are taken. Based on TLC analysis of each fraction, fractions 8-21 are pooled and concentrated to afford 396 mg (50.8% yield) of the title compound as a white solid: 13C-NMR (ds-acetone) 172.0, 157.2, 156.5, 138.1, 136.4, 129.1, 128.8, 128.3, 128.1, 96.6, 93.7, 74.5, 72.1, 67.1, 66.7, 66.5, 65.2, 60.0, 57.5, 53.7, 50.5, 44.0, 31.6, and 21.5 ppm. Exact mass calc'd for Cs1H78NbOlbSi4 (tetra TMS): 1052.4611. Found: 1052.4601. Example 69 3'-(R)-3'-[(carboxymethyl)aminomethyl] dihydrospectino mycin trihydrochloride. Refer to Chart F. In 10 ml of methanol is dissolved 390 mg (0.5 mmol) of N,N'dibenzyloxycarbonyl-3'-(R)-3'-[(benzyloxycarbonylmethyl)aminomethyl] dihydrospectinomycin (Example 68). To this solution is added.390 mg of palladium black followed by 0.2 ml (5.0 mmol) of formic acid. The reaction is stirred for 20 min and an additional 0.1 ml (2.5 mmol) of formic acid is added. After stirring for 1.5 hr, the reaction is filtered thru celite and concentrated in vacuo to afford 328 mg of a white solid. The product is taken up in water and treated with 2 ml of 1N hydrochloric acid. The solution is frozen and lyophilized to afford 237 mg (84.5% yield) of a white solid: IJC-NMR (D20) 170.9, 94.2, 93.5, 73.2, 70.6, 68.3, 67.0, 66.3, 62.6, 60.7, 59.4, 52.0, 50.8, 41.5, 31.9, 31.5, and 21.1 ppm; exact mass calc'd for Cb2H7lNdOySis (penta TMS) 781.4036. Found: 781.4063. Example 70 N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N-acetylamino- methyl) dihydrospectinomycin (Formula LXXXVIII: R45 is methyl). Refer to Chart F. To a solution of 631 mg (1.0 mmol) of N,N'-dibenzyloxycarbonyl- 3'-(R)-3'-aminomethyldihydrospectinomycin in 4 ml of methanol stirred at 0 under a nitrogen atmosphere is added 0.15 ml (1.1 mmol) of triethylamine and 0.10 ml (1.1 mmol) of acetic anhydride. The mixture is stirred 1.15 hr at 0 , and then concentrated in vacuo. The residue is dissolved in 35 ml of ethyl acetate and washed twice with 5 ml of water, once with 20 ml of brine and dried over MgSO4. Removal of solvent in vacuo affords 600 mg of white solid. The product is purified by chromatography on 40 9 of 230-400 mesh silica gel packed with 1% methanol/chloroform and eluted with 1 1 of 1; methanol/chloroform, 2 1 of 2% methanol/chloroform and finally 3% methanol/chloroform, taking 45 ml fractions. Fractions 71-98 are pooled and concentrated to give 212 mg (0.32 mmol, 32%) of title product as a white solid: 13C-NMR (d6-acetone) 6 171.7, 157.0, 138.2, 129.1, 128.4, 95.0, 93.3, 75.8, 74.5, 67.7, 67.4, 70.0, 66.6, 60.0, 57.0, 42.2, 39.6, 31.8, 22.9, and 21.5; MS exact mass for pentatrimethylsilyl derivative C48HNjO1,Si5. Calc'd: 1033.4823. Found: 1033.4807. Example 71 3'-(R)-3'-(acetylaminomethyl)-dihydrospectinomycin dihydrochloride. Refer to Chart F. To a solution of 205 mg (0.30 mmol) of the title product of Example 70 in 5 ml of methanol is added 200 mg of palladium black and 0.11 ml (3.0 mmol) of formic acid. The mixture is stirred 30 min at room temperature, filtered and concentrated in vacuo. The residue is dissolved in 5 ml of H20, treated with 0.6 ml (0.6 mmol) of 1.0 N HCl and lyophilized to afford 200 mg of white solid: 13C-NMR (D > O, CH CN internal reference) 6 175.5, 94.3, 93.4, 76.1, 70.5, 68.7, 66.9, 65.9, 62.4, 60.5, 59.2, 42.6, 39.1, 31.9, 31.3, 22.8, and 21.0; MS exact mass for hexatrimethylsilyl derivative Cj5H79Nb08Si6. Calc'd: 837.4483. Found: 837.4472. Example 72 3'-(R)-3'-[N-glycylaminomethyl]-dihydrospectinomycin trihydrochloride Refer to Chart F. A. To a solution of 185 mg (0.29 mmoi) of N,N'-dibenzyloxy carbonyl-3'-(R)-3'-aminomethyldihydrospectinomycin (Example 52) in 10 ml of dry tetrahydrofuran is added 60 mg (0.29 mmol) of N-benzyloxycarbonylglycine, 60 mg (0.29 mmol) of dicyclohexylcarbodiimide and 10 mg (0.08 mmol) of 4-dimethylaminopyridine. The mixture is stirred 5 hr at room temperature, concentrated in vacuo and partitioned between 100 ml of ethyl acetate and 10 ml of H20. The ethyl acetate layer is dried with brine and MgSO4 and concentrated in vacuo to give 230 mg of white solid. The product is chromatographed on 20 9 of 230-400 mesh silica gel packed with 1% methanol/chloroform and eluted with 500 ml of 1%, 500 ml of 2S, and 1 1 of 2.5% methanol/chloroform. The pure fractions, as determined by TLC on silica gel (10% methanol/chloroform, Rf = 0.32) are pooled to afford 112 mg (0.14 mmol, 47%) of the product as a white solid: 18C-NMR (d > -acetone) 6 171.0, 158.0, 138.2, 128.6, 128.5, 128.3, 95.1, 93.3, 75.8, 74.5, 67.3, 67.0, 66.5, 66.4, 60.5, 57.5, 45.0, 42.4, 39.7, 31.8, and 21.4; MS (tetrakistrimethylsilyl derivative) 1110, 1095, 1002, 987, 889, 818, 745, 493, 449, 359, 329, 305, 257, 91; exact mass, for M+, Cs3H8zN40l4Si4. Calc'd: 1110.4904. Found: 1110.4841. B. To a solution of 110 mg (0.13 mmol) of the reaction product of part A in 5 ml of methyl alcohol is added 100 mg of palladium black and 50 pl (1.34 mmol) of formic acid. The mixture is stirred 35 min at room temperature, filtered and concentrated in vacuo. The residue is dissolved in 5 ml of HzO, treated with 0.45 ml (0.45 mmol) of 1 N HCl and lyophilized to give 70 mg (0.12 mmol, 92%) of title product as a white solid: 13C-NMR (D20, CH3CN internal reference) 6 168.3, 94.4, 93.5, 76.0, 70.7, 68.8, 67.0, 66.1, 62.6, 60.6, 59.4, 42.6, 41.6, 39.3, 32.0, 31.4, and 21.1; MS exact mass for M+-CHb for heptatrimethylsilyl derivative, C38H88N4O8Si7. Calc'd: 924.4987. Found: 924.4989. Example 73 3'-(R)-3'-[N-(pyrolle-2-carbonyl )aminomethyl]-dihydro spectinomycin dihydrochloride. Refer to Chart F. A. To a solution of 631 mg (1.0 mmol) of N,N'-dibenzyloxycarbonyl-3'-(R)-3'-aminomethyldihydrospectinomycin (Example 52) in 20 ml of dry tetrahydrofuran stirred at room temperature with a nitrogen atmosphere is added 216 mg (1.05 mmol) of dicyclohexylcarbodiimide, 10 mg (0.08 mmol) of 4-dimethylaminopyridine and 111 mg (1.0 mmol) of pyrolle-2-carboxylic acid. The mixture is stirred 2 hr at room temperture and 4 equivalents of each of the last three reactants are added. After 2 hr stirring, the mixture is concentrated in vacuo, diluted with 200 ml of EtOAc and extracted with 50 ml of 5% NaHCO. Some insoluble material is removed with the aqueous layer. The EtOAc solution is washed with 5% NaHCO3 and brine and dried with MgSO. Concentration in vacuo affords 1.43 g of brown gum. The product is chromatographed on 140 g of 230-400 mesh silica gel pcked with 1; methanol/chloroform and eluted with 1 1 of 1% methanol/chloroform and the remainder 2% methanol/chloroform collecting 45 ml fractions. Fractions 105-154 are pooled to afford 252 mg (0.35 mmol, 35X) of the product as a white solid: 13C-NMR (dÓ-acetone) Ï 162.8, 157.0, 138.2, 129.1, 128.4, 126.6, 122.6, 111.0, liO.O, 95.2, 93.4, 76.1, 74.5, 67.4, 66.5, 65.6, 60.0, 57.8, 55.4, 42.5, 40.0, 31.5, and 21.4; MS for pentatrimethylsilyl ether 1084, 1069, 997, 889, 799, 339, 195, 166, 91; exact mass for C51H4N4O12Si5. Oalc'd: 1084.4932. Found, 1084.4927. B. To a solution of 240 mg (0.33 mmol) of the reaction product of part A in 5 ml of methanol is added 200 mg of palladium black and 0.125 ml (3.3 mmol) of formic acid. The mixture is stirred 30 min at room temperature, filtered and concentrated in vacuo. The residue is dissolved in 5 ml of H20, trated with 0.66 ml (0.66 mmol) of 1N HCl and lyophilized to afford 174 mg of the title product as a white solid: 13C-NMR (D20, CH3CN internal reference) 6 164.3, 125.4, 124.2, 113.0, 110.8, 94.4, 93.7, 76.6, 70.7, 68.9, 67.1, 66.1, 62.6, 60.6, 59.4, 42.6, 39.3, 32.0, 31.4, and 21.4; MS exact mass for heptatrimethylsilyl ether C41H88N4O8Si7. Calc'd: 960.4987. Found, 960.4982. Example 74 N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(succinylamino- methyl) dihydrospectinomycin (Formula LXXXVIII: R45 is -CH2CHzCOOH). Refer to Chart F. In 0.5 ml of methanol are combined 100 mg (0.15 mmol) of N,N'dibenzyloxycarbonyl-3'-(R)-3'-(aminomethyl) dihydrospectinomycin (Example 52), 16.5 mg (0.165 mmol) of succinic anhydride and 23 ul (0.165 mmol) of triethylamine. The solution is stirred for 1 hr and concentrated in vacuo. The residue is partitioned between ethyl acetate and water. The water is acidified with concentrated hydrochloric acid and the ethyl acetate is separated. After extracting a second time with ethyl acetate, the extracts are combined, washed with brine, and dried over magnesium sulfate. After filtering, the solvent is removed in vacuo to afford 100 mg of a white solid (91.2% yield): 13C-NMR (d6-acetone) 174.5, 173.5, 157.5, 138.3, 129.2, 128.5, 128.3, 95.3, 93.4, 76.0, 74.8, 74.5, 67.9, 67.4, 66.4, 65.4, 60.5, 60.4, 57.6, 42.7, 39.8, 31.8, 30.8, and 21.4 ppm. Example 75 3'-(R)-3'-(succinylaminornethyl)dihydrospectinomycin trihydrochloride Refer to Chart F. In 5 ml of methanol is dissolved 80 mg (0.10 mmol) of N,N' dibenzyloxyCarbonyl-3'-(R)-3'-(succinylaminomethyl)dihydrospectino- mycin (Example 74). To this solution is added 75 mg of palladium black followed by 27 ul (0.69 mmol) of formic acid. After stirring for 40 min, the reaction is filtered and the solvent is removed in vacuo to afford 63 mg of a white solid. The product is taken up in water and treated with 1 ml of 1N hydrochloric acid. The solution is frozen and lyophilized to afford 58 mg (100; yield) of the title compound as a white solid: 1dC-NMR (D20) 177.7, 176.2, 94.4, 93.6, 76.4, 70.7, 69.0, 67.0, 66.1, 62.6, 60.6, 59.4, 42.6, 39.0, 32.0, 31.4, 31.2, 30.3, and 21.0 ppm; exact mass calc'd for C40H89N301oSi7 (hepta TMS): 967.4933. Found: 967.4953. Example 76 N,N'-di-benzyloxycarbonyi-3'-(S)-3'-(N-ethylamino- methyl) dihydrospectinomycin (Formula LXV: R is hydrogen and R64 is ethyl). Refer to Chart F. In 6 ml of MeOH are combined 500 mg (0.774 mmol) of N,N'-dibenzyloxycarbonyl-3'-(S)-3'-(aminomethyl) dihydrospectinomycin (Example 50), 44 ijl (0.774 mmol) of acetaldehyde and a trace of methyl orange indicator in MeOH. To this solution is then added 16.2 mg (0.258 mmol, 0.774 mmol H ) of NaCNBH3 in 1 ml of MeOH. The pH is adjusted with the addition of 1N methanolic HCl until the indicator is just pink. The reaction is then stirred at room temperature and additional 1N HCl/MeOH is added to keep the indicator pink. After 2.5 hours the MeOH is removed and the residue partitioned between H20 and EtOAc. The aqueous phase is extracted again with EtOAc (2 x 30 ml). The combined organics are washed with brine (1 x 50 ml) and dried over MgSO4. After filtering, the solvent is removed in vacuo to afford 458 mg of a white solid. The product is taken up in CHCl3 and chromatographed on 20 gm of silica gel, slurry packed in CHC13. The column is eluted as follows: 100 ml, 1% MeOH/CHCl; 100 ml, 2 MeOH/CHClj, 100 ml 3% MeOH/CHCl; 100 ml 5% MeOH/CHCl; 100 ml 7% MeOH/CHCl; and 700 ml 10X MeOH/CHCl3. In elution volume 520-720 ml there is contained 306 mg of the title compound as a white solid (60% yield 3C-NMR (d6-acetone) 138.1, 129.1, 128.3, 94.2, 74.4, 73.1, 67.2, 66.6, 65.1, 57.6, 57.5, 57.3, 55.7, 45.0, 40.3, 31.4, 21.1, and 15.3 ppm; exact mass calc'd for C41H66N3O11Si3 (tri-OTMS,-CH3) 860.4005, found 860.4008. Example 77 N,N'-di-benzyloxycarbonyl-3'-(S)-3'-(N-butylamino- methyl) dihydrospectinomycin (Formula LXV: R63 is hydrogen and R64 is n-butyl). Refer to Chart F. In 10 ml of MeOH is dissolved 507 mg (0.803 mmol) of N,N'-di- benzyloxycarbonyl-3'-(S)-3'-(aminomethyl) dihydrospectinomycin. Example 50. To this solution is added 0.71 ml (8.0 mmol) of nbutyraldenyde and a drop of methyl orange indicator in MeOH. This is followed by the addition of 17 mg of NaCNBH3 in 1 ml of MeOH. The pH is adjusted to 4 with the addition of 1N HCl/MeOH. The pH is maintained at 4 for 0.5 hr while the reaction is stirred. The MeOH is then removed in vacuo and the residue partioned between EtOAC and H20. The EtOAC is separated and combined with 1, 25 ml EtOAC extract of the aqueous phase. The combined extracts are washed with 50 ml of brine and dried over MgSO4. After filtering, removal cf the solvent affords 616 mg of a white solid. The product is taken up in CHCl3 and chromatographed on 30 g of silica gel, slurry packed in CHC13. The column is eluted as follows: 100 ml 1% MeOH/CHCl3; 100 ml 2% MeOH/CHCl; 100 ml 3% MeOH/CHCl 3; 100 ml 4% MeOH/CHCl 3; 1.3 1 5% MeOH/CHCl. In elution volution volume 850-1400 ml there is recovered 250 mg of the title compound as a white solid: (45.3% yield): 13C NMR (d6-acetone) 138.2, 129.2, 128.4, 94.2, 74.5, 73.1, 67.3, 66.7, 65.2, 57.6, 57.5, 55.9, 50.5, 40.3, 32.5, 31.6, 21.2, 20.9, and 14.2 ppm; exact mass calc'd for C46H78N3O11Si4 (tetra TMS-CH3) 960.4713, found 960.4722. Example 78 N,N'-di-benzyloxycarbonyl-3'-(S)-3'-(N-octylamino methyl) dihydrospectinomycin (Formula LXV: R63 is hydrogen and R64 is n-octyl). Refer to Chart F. In 5 ml of MeOH is dissolved 500 mg (0.79 mmol) of N,N'-di benzyloxycarbonyl-3'-(S)-3'-(aminomethyl) dihydrospectinomycin, Example 50. To this solution is added 1.23 ml of n-octanal and a drop of methyl orange/ MeOH solution. Then 17 mg of NaCNBHi in 1 ml of MeOH is added. The pH lowered to 4 with 1N HCl/MeOH. The reaction is stirred for 1 hr, maintaining the pH at 4. The MeOH is then removed in vacuo and the residue is taken up in CHCl. The solution is washed with 50 ml of brine and dried over MgS04. After filtering, the solvent is removed to afford an oil. The product is taken up in CHCl3 and chromatographed on 30 9 of silica, slurry packed in CHCl. The column is eluted as follows: 200 ml CHCl; 500 ml 1% MeOH/CHCl3; 1 1 2% MeOH/CHCl3; 500 ml 3% MeOH/CHCl; 1 1 5% MeOH/CHCl. In elution volume 1100-1400 ml there is recovered 186 mg of the title compound as a white solid (32P yield): 1jC-NMR (d6-acetone) 138.2, 129.2, 128.4, 94.2, 74.5, 74.2, 74.1, 72.9, 67.3, 66.7, 66.5, 65.2, 61.4, 61.1, 60.6, 60.5, 57.6, 57.4, 55.8, 50.8, 40.4, 32.4, 31.5, 30.8, 30.3, 30.1, 29.9, 27.8, 23.2, 21.2, and 14.3 ppm; exact mass calc'd for C51H89N3O11Si4 (tetra TMS) 1031.5574, found 1031.5585. Example 79 3'-(S)-3'-(N-ethylaminomethyl) dihydrospectinomycin trihydrochloride Refer to Chart F. In 10 ml of MeOH are combined 294 mg (0.44 mmol) of N,N'-dibenzyloxycarbonyl-3'-(S)-3'-(N-ethylaminomethyl) dihydrospectinomycin (Example 76) and 200 mg of Pd black. To this solution is added 170 ul of formic acid. The reaction is stirred for 40 minutes and is filtered. Removal of the solvent in vacuo affords 225 mg of a white solid. The product is dissolved in 2 ml of H20 and 1.5 ml of 1N HCl is added. The solution is frozen and lyophilized to afford 215 mg of a white solid (97.5% yield): 13C-NMR (D20) 96.3, 95.1, 75.5, 74.2, 70.6, 70.5, 70.3, 65.5, 65.0, 62.2, 54.5, 47.6, 41.7, 35.3, 34.6, 23.2, and 13.79 ppm; exact mass calc'd for C35H81N3O7Si6 (hexa TMS) 823.4690, found 823.4690. Example 80 3'-(S)-3'-(N-butylaminomethyl) dihydrospectinomycin trihydrochloride Refer to Chart F. In 10 ml of MeOH is dissolved 245 mg (0.39 mmol) of N,N'-dibenzyloxycarbonyl-3'-(S)-3'-(N-butylaminomethyl) dihydrospectinomycin (Example 77). To this solution is added 250 mg of Pd black followed by 152 ijl of HCOOH. The reaction is stirred for 45 min and is filtered. Removal of the solvent in vacuo affords 195 mg of a white solid. The material is taken Up in 2 ml of H20 and 1.5 ml of 1N HCl is added. The solution is frozen and lyophilized to afford 166 mg of a white solid (80% yield): 1dC-NMR (D20) 96.2, 95.3, 75.6, 73.4, 70.8, 69.7, 69.5, 65.1, 63.9, 61.7, 54.9, 52.4, 41.7, 34.8, 34.6, 30.8, 23.4, 22.9, and 16.6 ppm; exact mass calc'd for Cz7H85N30?Si6 (Hexas-TMS) 851.5003, found 851.4980; exact mass calc'd for C36H82N3O7Si6 (Hexa-TMS-CH) 836.4768, found 836.4757. Example 81 3'-(S)-3'-(N-octylaminomethyl) dihydrospectinomycin tri hydrochloride Refer to Chart F. In 5 ml of MeOH is dissolved 180 mg of N,N'-di-benzyloxycarbonyl3'-(S)-3'-(N-octylaminomethyl) dihydrospectinomycin (Example 78). To this solution is added 200 mg of Pd black followed by 94 ul of HCOOH. The reaction is stirred for 30 min and is filtered. The solvent is removed in vacuo to afford 150 mg of a white solid. The product is taken up in 2 ml of H2O and 0.8 m7 of 1N HCL is added. The solution is frozen and lyophilized overnight to afford 135 mg of a white solid (96X yield): 13C-NMR (duo) 96.2, 95.3, 75.6, 73.4, 70.6, 69.7, 69.5, 65.1, 63.9, 61.7, 54.9, 50.7, 41.8, 34.8, 34.6, 32.0, 29.5, 28.8, 25.8, 23.4, and 17.2 ppm; exact mass calc'd for C41H9sN307Si6 (hexa TMS) 907.5629, found 907.5618. Example 82 Procedure for the Preparation of 3-(R)-3'-(N alkylated) dihydrospectinomycins A. For predominant monoalkylation, N,N '-dibenzyloxycarbonyl-3 '- (R)-3'-(aminomethyl) dihydrospectinomycin (Example 52) is dissolved in MeOH. To the solution is added 10 equivalents of the appropriate aldehyde and a trace of methyl orange indicator. The pH is then adjusted to the indicator's endpoint with methanolic HCl and 0.33 equivalents of NaCNBH3 in MeOH is added. The reaction is stirred at room temperature and the pH is maintained near the endpoint of methyl orange by adding additional methanolic HCl. The reaction is easily followed by TLC using Analtech Silica plates and eluting with 10% MeOH/CHCl3/1% NH40H as a solvent. When the reaction is complete, the solvent is removed in vacuo and the residue is partitioned between H20 and EtOAc. The aqueous phase is made alkaline with the addition of concentrated NH4OH and the EtOAc is separated and combined with an additional EtOAc extract. The combined extracts are washed with brine and dried over MgSO4. The solvent is then removed in vacuo to afford the crude product. The product is taken up in CHClj and chromatographed on silica, slurry packed in CHCl. The column is eluted with a MeOH/CHClj gradient (1%-5%), and 50 ml fractions are taken. The fractions are analyzed by TLC and pure fractions are pooled and concentrated in vacuo to afford the product. B. For predominant dialkylation, the above procedure is followed using 0.66 equivalents of NaCNBH. According to the procedure above, there are prepared (a) N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N-ethylaminomethyl) dihydrospectinomycin: Alkylation of 491 mg (0.78 mmol) of N,N'dibenzyloxycarbonyl-3'-(R)-3'-(aminomethyl) dihydrospectinomycin affords 123 mg (24% yield) of the title compound after chromatography: 1JC-NMR (d6-acetone) 138.1, 129.1, 128.3, 128.1, 97.0, 93.8, 74.5, 71.6, 67.1, 66.4, 65.2, 57.6, 54.0, 44.4, 43.8, 31.6, 21.5 and 14.9 ppm; exact mass calc'd for C4sH77N301lSis (tetra TMS) 947.4653, found 947.4601. (b) N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N-propylaminomethyl) dihydrospectinomycin: Alkylation of 1.7 g (2.7 mmol) of amine affords 1.1 g of the title product after chromatography (61% yield): 13C-NMR (db-acetone) 158.0, 157.0, 138.1, 129.1, 128.3, 128.1, 97.1, 93.8, 74.5, 71.6, 67.2, 66.4, 65.2, 57.6, 54.3, 51.5, 48.9, 44.5, 31.8, 31.6, 23.0, 21.5, and 11.9 ppm; exact mass calc'd for C46H79N3O11Si4 (tetra TMS) 961.4791, found 961.4789. (c) N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N-pentylaminomethyl) dihydrospectinomycin: Alkylation of 2.0 g (3.16 mmol) of amine affords 653 mg of the title compound after chromatography (29 yield): 13C-NMR (d6-acetone) 138.2, 129.1, 128.3, 128.1, 97.1, 93.8, 74.6, 71.7, 67.2, 66.5, 65.2, 61.0, 60.9, 57.7, 54.4, 49.7, 44.5, 31.6, 30.0, 29.7, 23.0, 21.5, and 14.3 ppm; exact mass calc'd for C4bHbbNbO1lSi4 (tetra TMS) 989.5104, found 989.5113. (d) N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N-hexylaminomethyl) dihydrospectinomycin: Alkylation of 500 mg (0.79 mmol) of amine using an excess of NaCNBH3 affords a mixture of mono and dialkylated products. The mixture is chromatographed to afford 109 mg (19; yield) of mono alkylated product: 13C-NMR (0,-acetone) 138.1, 129.1, 128.3, 128.1, 97.0, 93.8, 74.5, 71.7, 67.2, 66.4, 65.2, 57.6, 54.3, 49.7, 44.4, 32.2, 31.6, 29.9, 27.4, 23.1, 21.5, and 14.2 ppm; exact mass calc'd for C49H85N3O11Si4 (tetra TMS) 1003.5261, found 1003.5278; and 310 mg (49% yield) of dialkylated product: 13C-NMR (d6-acetone) 138.2, 129.1, 128.7, 128.4, 128.2, 97.2, 93.8, 74.7, 74.4, 72.2, 67.2, 66.5, 65.4, 65.2, 61.0, 60.4, 60.3, 59.7, 57.7, 55.9, 44.6, 32.2, 32.0, 31.8, 31.5, 27.6, 26.9, 23.2, 21.5, and 14.3 ppm; exact mass calc'd for C34H94N3O11Si4 (tetra TMS-CH3) 1072.5965, found 1072.5968. (e) N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N-octylaminomethyl) dihydrospectinomycin: Alkylation of 2.3 g (3.6 mmol) of amine affords 1.65 g of the title compound after chromatography (62% yield); 13C-NMR (d6-acetone) 157.7, 157.6, 138.1, 129.1, 128.3, 128.1, 97.1, 93.7, 74.5, 74.6, 73.8, 71.6, 67.1, 66.4, 65.2, 61.1, 60.9, 60.8, 57.6, 54.4, 49.7, 44.5, 32.4, 31.6, 30.0, 29.8, 27.8, 23.2, 21.5, and 14.3 ppm; exact mass calc'd for C,,H,,N,O,1SI, (tetra B4S-CH) 1016.5339, found 1016.5327. (f) N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N-isobutylaminomethyl) dihydrospectinomycin: Alkylation of 500 mg (0.79 mmol) of amine affords 216 mg of the title compound after chromatography (39.8% yield): 13C-NMR (d6-acetone): 138.1, 129.1, 128.6, 128.3, 128.1, 97.1, 93.8, 74.5, 71.7, 67.2, 66.4, 65.2, 57.3, 54.6, 44.4, 31.8, 31.6, 28.4, 21.5, 20.9, and 20.8 ppm. Exact mass calc'd for C7H1NdO11Si4 (tetra TMS) 975.4948, found 975.4943. (g) N,N'-dibenzyloxycarbonyl-3'-(R)-3'-[N-(2-methyl butyl)amino methyl] dihydrospectinomycin: Alkylation of 2.0 g (3.16 mmol) of amine affords 478 mg of the title compound after chromatography (21.6% yield): 13C-NMR (d6-acetone) 138.2, 129.1, 128.4, 128.2, 97.1, 93.8, 74.6, 71.6, 67.2, 66.5, 65.3, 61.1, 61.0, 60.3, 57.7, 56.0, 54.8, 44.6, 35.0, 31.6, 28.0, 26.7, 21.6, 17.9, and 11.5 ppm; exact mass calc d for C47H80N3O11Si4 (tetra TMS-CH) 974.4870, found 974.4859. (h) N,N'-dibenzyloxycarbonyl-3'-(R)-3'-[N-cyclohexylmethyl)aminomethyl] dihydrospectinomycin: Alkylation of 2.47 g (3.9 mmol) of amine affords 982 mg of the title compound as a white solid (30.6X yield): 13C-NMR (d6-acetone) 138.1, 129.1, 128.3, 97.0, 93.7, 74.5, 71.7, 67.2, 66.5, 65.2, 57.6, 56.5, 54.6, 44.5, 38.0, 31.9, 31.6, 27.2, 26.5, and 21.5 ppm; exact mass calc'd for C50Hs5N30llSi4 (tetra TMS) 1015.5261, found 1015.5240. (i) N,Ni-dibenzyloxycarbonyl-3'-(R)-3'-[N-(cyclooctylmethyl)- aminomethyl] dihydrospectinomycin: Alkylation of 1.5 gm (2.27 mmol) of amine affords 729 mg of the title compound. Also recovered is 503 mg of unreacted amine. The yield of the title compound based on recovered amine is 61.3%: 13C-NMR (d6-acetone) 138.3, 129.1, 128.4, 128.2, 97.2, 93.8, 74.6, 71.8, 67.1, 67.0, 66.5, 65.3, 61.1, 61.0, 60.2, 57.7, 57.3, 54.7, 44.6, 37.7, 31.6, 31.5, 31.2, 27.7, 27.0, 26.1, 26.0 and 21.5 ppm; exact mass calc'd for C51H86N3O11Si4 (tetra TMS-CH) 1028.5339, found 1028.5255. (j) N,N'-dibenzyloxycarbonyl-3'-(R)-3'-[N,N-dicyclohexylmethyl)aminomethyl] dihydrospectinomycin: Dialkylation of 634 mg (1.0 mmol) of amine affords 173 mg of the title compound (21% yield): 13C-NMR (d-acetone) 129.1, 128.4, 128.2, 97.3, 93.5, 74.7, 72.9, 67.4, 67.2, 66.5, 65.1, 61.2, 57.7, 57.6, 57.4, 44.6, 36.5, 32.6, 32.4, 31.7, 27.2, 26.7, and 21.4 ppm; exact mass calc'd for C53H86N3O11Si3 (tri TMS-CH) 1024.5570, found 1024.5526. (k) N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N,N-diisobutylmainomethyl) dihydrospectinomycin: Dialkylation of 631 mg (1 mmol) of amine affords 171 mg of the title compound as a white solid (23 yield): 13C-NMR (d-acetone) 138.1, 129.1, 128.3, 128.1, 97.0, 93.5, 74.6, 73.1, 67.3, 67.2, 66.4, 65.2, 61.1, 57.5, 44.1, 31.4, 26.8, 21.7, and 21.4 ppm; exact mass calc'd for CHd1NdO11Si4 (tri-TMS) 959.5179, found, 959.5134. Example 83 Deprotection of N,N'-dibenzyloxycarbonyl-3'-(R)-3'-N mono and N,N-dialkylaminomethyl dihydrospectinomycins The protected substrate is dissolved in MeOH and an equivalent weight of Pd black is added. To this mixture is added 10 equivalents of formic acid. The reaction is stirred for 45 min, filtered and concentrated to dryness. The residue is taken up in H20 and 3.5 equivalents of 1N HCl are added. The solution is frozen and lyophilized to afford the final product. Accordingly, the products of Example 82 yield: (a) 3'-(R)-3'-(N-ethylaminomethyl) dihydrospectinomycin trihydrochloride: Deprotection of 123 mg (0.19 mmol) affords 83 mg (89% yield) of the title compound: 13C-NMR (D20) 94.0, 93.2, 73.2, 70.4, 68.2, 66.8, 66.2, 62.4, 60.5, 59.3, 50.5, 45.1, 40.7, 31.9, 31.5, 21.0, and 11.1 ppm; exact mass calc'd for C35H81N3O11Si6 (hexa TMS) 823.4690, found 823.4665. (b) 3'-(R)-3'-(N-propylaminomethyl) dihydrospectinomycin trihydrochloride: Deprotection of 1.1 gm (1.6 mmol) affords 0.68 gm of the title compound as a white solid (82.8% yield): 13C-NMR (D20) 94.1, 93.3, 73.3, 70.5, 68.2, 66.9, 66.2, 62.5, 60.6, 59.3, 51.2, 51.0, 41.0, 32.0, 31.6, 21.0, 19.5, and 11.2 ppm; exact mass calc'd for C3bHbuN307Si6 (hexa TMS) 837.4846, found 837.4867. (c) 3'-(R)-3'-(N-pentylaminomethyl) dihydrospectinomycin trihydrochloride: Deprotection of 650 mg (0.92 mmol) affords 573 mg of the title compound as a white solid: 13C-NMR (D20) 94.3, 93.5, 73.4, 70.9, 68.4, 67.1, 66.5, 62.7, 60.9, 59.6, 51.2, 49.8, 41.2, 31.9, 31.5, 28.9, 25.6, 22.5, 21.1, 20.8, and 14.2 ppm; exact mass calc'd for C38H87N07Sib (hexa TMS) 865.5159, found 865.5167. (d) 3'-(R)-3'-(N-hexylaminomethyl) dihydrospectinomycin trihydrochloride: Deprotection of 87 mg (0.12 mmol) afforded 58 mg (87 yield) of the title compound as a white solid: 13C-NMR (D20) 94.1, 93.3, 73.2, 70.5, 68.3, 66.9, 66.2, 62.5, 60.6, 59.3, 51.0, 49.8, 40.9, 31.9, 31.5, 31.4, 26.3, 25.8, 22.7, 21.0, and 14.3 pDm; exact mass calc'd for C39H89N3O7Si6 (hexa-TMS) 879.5316, found 879.5303. (e) 3'- (R)-3'-(N-octylaminomethyl) dihydrospectinomycin trihydrochloride: Deprotection of 1.65 g (2.2 mmol) affords 1.12 9 of the title compound as a white solid (87% yield): 13C-NMR (D20) 94.0, 93.2, 73.2, 70.4, 68.2, 66.8, 66.2, 62.4, 60.5, 59.2, 50.9, 49.7, 32.1, 31.9, 31.5, 29.3, 26.8, 25.8, 23.0, 20.9, and 14.5 ppm; exact mass calc'd for C41H93N3O11Si6 (hexa TMS) 907.5629, found 907.5627. (f) 3'-(R)-3'-(N-isobutylaminomethyl) dihydrospectinomycin trihydrochloride: Deprotection of 216 mg (0.29 mmol) affords 152 mg (90% yield) of the title compound as a white solid 13C-NMR (D2O9 93.9, 93.3, 73.0, 70.3, 68.1, 66.8, 66.1, 62.3, 60.5, 59.2, 56.3, 51.3, 41.2, 31.8, 31.4, 25.5, 21.0, 19.9, and 19.7 ppm; exact mass calc'd for C37H85N3O7Si6 (hexa TMS) 851.5003, found 851.5020. (9) 3'-(R3-3'-[N-(2-methylbuty')aminomethylzdihydrospectinomycin trihydrochloride: Deprotection of 478 mg (0.68 mmol) affords 338 mg of the title compound as a white solid (87% yield): 13C-NMR (D20) 94.0, 93.4, 73.0, 70.4, 68.2, 66.8, 66.2, 62.4, 60.5, 59.3, 55.1, 51.6, 51.5, 41.3, 31.8, 31.7, 31.5, 27.1, 21.0, 16.9, and 11.1 ppm; exact mass calc'd for C38H87N3O7Si6 (hexa TMS) 865.5159, found 865.5150. (h) 3'-(R)-3'-[N-cyclohexylmethyl)aminomethyl]dihydrospctinomycin trihydrochloride: Deportection of 928 mg (1.12 mmol) affords 640 mg of the title compound as a white solid (86% yield): 13C-NMR (D20) 94.2, 93.5, 73.2, 70.6, 68.3, 66.9, 66.3, 62.5, 60.6, 59.4, 55.3, 51.5, 41.3, 34.6, 31.9, 31.5, 30.7, 26.5, 25.9 and 21.0 ppm; eact mass calc'd for C40HgyNsO7Si6 (hexa TMS) 891.5315, found 891.5324. (i) 3'-(R)-3'-[N-(cyclooctylmethyl)aminomethyl]dihydrospectinomycin trihydrochloride: Deprotection of 792 mg (1.04 mmol) affords 550 mg of the title compound as a white solid (88.9% yield): 13C-NMR (D20, as the triformate) 94.4, 93.6, 73.2, 70.8, 68.4, 67.0, 66.4, 62.7, 60,8, 59.6, 55.9, 51.8, 41.7, 34.6, 31.9, 31.5, 30.0, 27.5, 26.8, 25.4 and 21.1 ppm; exact mass calc'd for C4,Hg3N3075i6 (hexa-ThS) 919.5629, found 919.5656. (j) 3'-(R)-3'-(N,N-dihexylaminomethyl)dihydrospectinomycin trihydrochloride: Deprotection of 220 mg (0.28 mmol) affords 157 mg (88 yield) of the title compound as a white solid: 13C-NMR (D20) 94.1, 93.3, 70.5, 68.3, 68.1, 66.7, 66.6, 66.5, 66.3, 62.4, 60.5, 59.3, 56.9, 56.7, 31.9, 31.5, 26.3, 23.7, 22.8, 21.0 and 14.4 ppm; exact mass calc'd for C42HN307Si6 (hexa TMS) 891.5860, found 891.5853. (k) 3'-(R)-3'-[N,N-(dicyclohexylmethyl)aminomethyl]dihydrospectinomycin trihydrochloride: Deprotection of 149 mg (0.18 mmol) affords 124 mg of the title compound as a white solid (100% yield): 13C-NMR (DzO) 94.3, 93.8, 73.2, 70.5, 68.2, 66.9, 66.5, 65.2, 54.5, 62.6, 60.7, 59.5, 43.2, 34.1, 33.7, 31.9, 31.8, 31.3, 30.9, 30.7, 26.5, 25.9 and 21.1 ppm; exact mass calc'd for C41H85N3O7Si4 (tetra TMS) 843.5465, found 843.5459. (1) 3'-(R)-3'-(N,N-diisobutylaminomethyl)dihydrospectinomycin trihydrochloride: Deprotection of 153 mg (0.20 mmol) affords 96 mg of the title compound (82% yield: 13C-NMR (D20) 94.3, 93.9, 73.3, 70.6, 68.2, 66.7, 66.6, 65.7, 62.6, 60.7, 59.6, 43.3, 31.9, 31.8, 31.6, 25.1, 24.8, 21.1, 21.0, 20.6, 20.4, 19.8 and 19.6 ppm; exact mass calc'd for C38H85N3O7Si5 (penta-TMS) 835.5234, found 835.5241. The hydrogenation and isomerization processes illustrated in Chart F can be carried out at any temperature at which reactants will be sufficiently soluble, in the solvent being used, at which reactants and products will not thermally decompose and at which the reaction will proceed at a rate acceptable to the person using the process. A person of ordinary skill can easily ascertain the limit of the temperature ranges for any combination of reactants for any solvent, base or basic ion-exchange resin and product. The preferred range is 20-300C. The isomerization reaction illustrated in Chart F is catalyzed by base or basic ion-exchange resin. In both the hydrocyanation and the isomerization, preferred bases, if used, are triethylamine and potassium or sodium carbonate. Preferred ion-exchange resin, if such resin is used, is Amberlite IRA-45 available from the Rohm and Maas Co. of Philadelphia, Pennsylvania. Most preferred in the isomerization reaction from 3'(R) to 3'(S) epimer and the hydrocyanation process wherein more of the 3'(S) epimer than of the 3'(R) epimer is desired, is potassium carbonate as base and methanol as solvent. Most preferred in the hydrocyanation reaction when more of the 3'(R) epimer than of the 3'(S) epimer is desired, is use of Amberlites IR-45 resin with methanol as solvent and at least a two-fold molar excess of acetone cyanohydrin as source of cyano groups. Removal of basic ion-exchange resin, or its neutralization with acid, or neutralization of base, if only base is used, slows the R to S isomerization drastically. "Quenching" means slowing sufficiently to permit the isolation of the R epimer and its stabilization by, for example, further reaction, before the ratio of the amount of R epimer to the amount of S epimer becomes less than 1. Whenever synthetic methods disclosed herein result in two or more compounds related as stereoisomers, such compounds will also be related as diasteriomers and consequently will have differing physical and chemical properties. These differing properties can be used to separate the stereoisomers from each other by any of numerous techniques known to the skilled in the art. As used in the present specification: "Basic ion-exchange resin" is ion-exchange resin wherein the ion-exchange groups are basic in character, i.e., acceptor of protons from or donors of electron pairs to compounds which pass or diffuse through the resin. Examples of basic ion-exchange resins wherein the ion-exchange groups are tertiary amino groups include the following: Amberlites IRA-45, IRA-68, IRA-93, and IRA-94, and Amberlysto A-21, all available from the Rohm and Haas Co. of Philadelphia, Pennsylvania; Dowers 3-X'4, available fom the Dow Chemical Co. of Midland, Michigan; and Dudlitee A-2, A-6, A-4F and A-7 available from the Diamond Shamrock Corp. of Cleveland, Ohio. "Halogen" means fluorine, chlorine, bromine or iodine. "Mcg" means "microgram" A compound which is a "source of cyano groups" means any compound which, under the basic reaction conditions, in the unreactive solvent employed in the hydrocyanation reaction illustrated in Chart F, will produce by, for example, decomposition or dissociation, a cyano group which can react with the 3' carbon of the spectinomycin or spectinomycin-analog starting material. Preferred source of cyano groups is acetone cyanohydrin. FORMULAS EMI82.1 FORMULAS (continued) EMI83.1 CH2=N+R5R6X6- VI EMI83.2 FORMULAS (continued) EMI84.1 FORMULAS (continued) EMI85.1 FORMULAS (continued) EMI86.1 FORMULAS (continued) EMI87.1 CHART A EMI88.1 CHART B EMI89.1 <tb> <SEP> j <SEP> G <SEP> 4 <tb> <SEP> ÒH <SEP> N2 <tb> <SEP> XLIII <tb> <SEP> < <SEP> no <SEP> \ <tb> <SEP> locking <tb> <SEP> on <tb> <SEP> ( <SEP> blocking <SEP> Zn <SEP> with <SEP> (blocking <tb> <SEP> YX <SEP> groups <SEP> on <tb> <SEP> XLIII) <SEP> H0/aceticgr0up5 <SEP> on <tb> <SEP> acid <SEP> XLIII) <tb> <SEP> LXXV <tb> <SEP> H <SEP> l <tb> X70 <SEP> LXXV <SEP> A <SEP> / <tb> <SEP> (deblocked) <tb> <SEP> on <SEP> or <SEP> Hdi <tb> <SEP> (Y=Ha <SEP> deblock <SEP> by <SEP> ; ; <tb> (all <SEP> blocking <SEP> \acidifir,ati <tb> <SEP> groups <SEP> must <SEP> be <SEP> conditions <SEP> LXXVI <SEP> I <tb> <SEP> removable <SEP> i?Y <SEP> or <SEP> \Weaonations <SEP> (blocked) <tb> acidification <tb> weakly <SEP> reducing <SEP> \ <tb> condtons, <SEP> e.g. <SEP> deblock <tb> <SEP> t-buoxcarSonyl <tb> <SEP> debl <SEP> ock <tb> <SEP> LXXVI <SEP> by <SEP> erdgcYng <SEP> , <tb> <SEP> deblok <SEP> by <SEP> acidi- <SEP> cone <tb> <SEP> fication <SEP> or <SEP> weakl <SEP> / <SEP> (e.g. <tb> <SEP> reducing <SEP> cataly'tic <SEP> H <SEP> H <tb> <SEP> conditions <SEP> z <SEP> Y=Cl) <SEP> hydrogenolysis) <tb> <SEP> (all <SEP> )blocking <SEP> LXXVIII <tb> <SEP> / <SEP> removable <SEP> by <SEP> (deblocked) <tb> <SEP> acidification <tb> <SEP> weakly <SEP> reducing <tb> <SEP> conditions, <SEP> e.g. <tb> <SEP> t-butoxycarbonyl <tb> <SEP> C1 <SEP> C <tb> <SEP> LXXIX <tb> CHART C EMI90.1 <tb> <SEP> OH <tb> <SEP> CHo <SEP> D <SEP> 3 <SEP> + <SEP> = <SEP> + <tb> <SEP> CH <SEP> - <SEP> CH2 <SEP> = <SEP> NRsRd(. <tb> <SEP> HO <SEP> N <SEP> bM0 <SEP> V <SEP> VI <tb> <SEP> N <SEP> N2 <tb> <SEP> C <SEP> \ <SEP> | <SEP> Tertiary <SEP> amine <SEP> base <tb> <SEP> H3 <SEP> Rv <SEP> l <SEP> solvent: <SEP> R8CN <tb> <SEP> OH <tb> <SEP> I <SEP> H <tb> <SEP> Ct4, <tb> <SEP> HO <SEP> H0 <SEP> IV <tb> <SEP> N <SEP> C(H)(NR5Rô) <tb> <SEP> 2 <tb> <SEP> I9/ <SEP> -- <tb> <SEP> 1. <SEP> 1. <SEP> NaCNBH, <SEP> 1. <SEP> NaA1H2(0(CH2) <SEP> zocH,] <tb> mildly <tb> <SEP> t <SEP> acidic <SEP> ons <tb> <SEP> - <SEP> conditions <tb> <SEP> ff <SEP> ' <SEP> XLIV <SEP> (pH <SEP> ¯ <SEP> 4) <SEP> or <tb> <SEP> 2. <SEP> Quench <SEP> with <SEP> I <SEP> 2. <SEP> Quench <SEP> with <SEP> H20 <tb> <SEP> 1. <SEP> mild <SEP> reducing <SEP> weak <SEP> acid <SEP> | <SEP> followed <SEP> with <tb> <SEP> agent <SEP> e.g., <SEP> weak <SEP> acid <SEP> 6) <SEP> ethyl <SEP> acetate <tb> 25 <SEP> l <SEP> NaBH4) <tb> <SEP> 2. <SEP> Quench <SEP> with <tb> <SEP> weak <SEP> acid <SEP> <tb> <SEP> (pKa <SEP> > 6 <tb> <SEP> · <SEP> + <SEP> or <SEP> 4W <tb> <SEP> 30 <SEP> CM2 <SEP> CH2 <SEP> H <SEP> CH2 <tb> <SEP> XLV <SEP> 'NR5R6 <SEP> Xi?RI5R6 <tb> <SEP> H <SEP> CM20H <tb> <SEP> XLVII <tb> <SEP> dieblock <SEP> deblock <tb> <SEP> 35 <SEP> > <SEP> r <tb> CHART D EMI91.1 <tb> <SEP> OsOn <SEP> oxidation <SEP> ¯t <SEP> XLV <tb> <SEP> CH2 <tb> <SEP> 5tereospecific) <tb> <SEP> ·¸in(enoHt2O2 <SEP> epoxidation <tb> vanadium <SEP> IV <tb> <SEP> HO <SEP> H2OH <SEP> epoxidation <tb> <SEP> (stereo <tb> <SEP> XLIX <SEP> specific <tb> <SEP> to <SEP> LI) <tb> <SEP> O <SEP> CH2 <SEP> CH2 <SEP> 0 <tb> <SEP> ,deHock <SEP> ¯¯¯ <SEP> CH2 <SEP> LTI <tb> <SEP> R61R62NH <SEP> LI <SEP> LII <tb> <SEP> OH <SEP> C,H2 <tb> <SEP> ce <tb> <SEP> LVIZ <SEP> 0Sk <SEP> R62 <SEP> O <SEP> siS <tb> <SEP> c <tb> <SEP> Cow <SEP> block <tb> <SEP> e <SEP> P <SEP> " <tb> <SEP> HO <SEP> CH2N3 <SEP> .' <SEP> CH2Nq <SEP> OH <SEP> NR61R62 <tb> <SEP> LIII <SEP> LIV <SEP> LVIII <tb> <SEP> u <tb> <SEP> I <SEP> deblock <tb> <SEP> < <SEP> CH2CN <SEP> OH <tb> <SEP> ,deblock <SEP> o <SEP> CH <SEP> LVI <tb> <SEP> HO <tb> <SEP> LV <tb> <SEP> reduction <tb> <SEP> (e.g., <SEP> PtO2/H2 <SEP> or <tb> <SEP> reduction <SEP> Raney <SEP> nickel/H2 <tb> <SEP> (e.g., <SEP> PtO2/H2or <SEP> in <SEP> presence <SEP> of <tb> <SEP> Raney <SEP> nickel/H2 <SEP> acetic <SEP> acid <tb> <SEP> in <SEP> presence <SEP> of <tb> <SEP> acetic <SEP> acid) <tb> i <tb> CHART D(contd) EMI92.1 > r <SEP> v <SEP> deblock <tb> ,deblock <SEP> " <SEP> / <SEP> deblock <tb> ebl <SEP> ock <tb> <SEP> LXIX <SEP> CH2CH2NH2 <SEP> LXX <tb> <SEP> reductive <SEP> reductive <tb> <SEP> al <SEP> kylation <SEP> alkylation <tb> <SEP> fi: <SEP> OH <SEP> debock <SEP> 3 <tb> ¯ <SEP> · <SEP> 'Y0H <tb> <SEP> debl <SEP> ock <SEP> HO <SEP> CH2CH2NR6R64 <SEP> deblock <tb> <SEP> CH2CH2NR636 <tb> <SEP> LXXI <SEP> LXXII <tb> CHART E EMI93.1 <tb> <SEP> I <SEP> LIV <tb> <SEP> H <SEP> t <SEP> CH2N3 <SEP> LIII <tb> <SEP> Pd <SEP> Pd <SEP> black/HCO2H <SEP> Pd <SEP> blackl <tb> <SEP> HCO2H <tb> <SEP> 2 <SEP> Cl <SEP> 2 <SEP> HCl <tb> <SEP> X <SEP> CH2NH2 <SEP> OH <tb> <SEP> HO <SEP> CH2NH2 <tb> <SEP> LXI <SEP> LXII <tb> PtOJ <SEP> H2 <SEP> v <SEP> s <SEP> PtO2/H2 <tb> <SEP> deblock <SEP> deblock <SEP> <tb> <SEP> I <tb> <SEP> HO <SEP> CH2NH2 <tb> <SEP> LXIII <SEP> LXIV <tb> <SEP> reductive <SEP> reductive <tb> <SEP> al <SEP> kylation <SEP> ,lkylation <tb> <SEP> , <SEP> deblock <tb> ,deblock <SEP> > <SEP> " <SEP> ) <tb> <SEP> HO <SEP> \ <SEP> CH2NR63R64 <SEP> CH2NR63P64 <SEP> OH <tb> <SEP> LXV <SEP> LXVI <tb> CHART F EMI94.1 <tb> <SEP> OH <tb> <SEP> R1 <SEP> ' <SEP> .0 <tb> <SEP> CHN <tb> <SEP> 0 <SEP> OH <SEP> VIII <tb> <SEP> <SEP> NC3 <tb> <SEP> R, <tb> <SEP> 1) <SEP> Hydrocyanation <tb> <SEP> 2) <SEP> Quench <SEP> with <SEP> acid <SEP> or <tb> <SEP> removal <SEP> of <SEP> resin <tb> deblock <SEP> 3' <SEP> ¯¯¯¯¯¯¯¯¯¯¯ <SEP> / <SEP> 3'3' <SEP> deblock <tb> != <SEP> =, <SEP> 2-4 <SEP> b,act <SEP> D <SEP> se <SEP> or <SEP> : <SEP> (e.g., <SEP> Pd <SEP> black <tb> .rith <SEP> SCC2Y" <SEP> asic <SEP> ion- <SEP> C'. <SEP> with <SEP> HCO2H) <tb> <SEP> exchange <tb> <SEP> resin <tb> <SEP> LXVII <SEP> LXVIII <tb> <SEP> Pt02/H2 <SEP> or <tb> <SEP> Raney <SEP> nickel/H2 <tb> <SEP> in <SEP> presence <SEP> of <tb> <SEP> acetic <SEP> acid <tb> <SEP> 3' <tb> <SEP> · <SEP> ThOH <tb> <SEP> OH <SEP> CH2NH2 <SEP> CH2NH2 <tb> <SEP> LXII <SEP> LXIII <SEP> I <SEP> g <SEP> LXIV <tb> <SEP> reductive <SEP> o <SEP> I <SEP> reductive <tb> <SEP> alkylation <SEP> / <SEP> µ <SEP> \ <SEP> alkylation <tb> <SEP> CH2 <SEP> ThH <tb> <SEP> b\ <SEP> > <SEP> HO <SEP> ICH2 <SEP> | <SEP> i <SEP> CH2NR63R64 <tb> <SEP> LXV <SEP> NR63RGLL <SEP> LXVI <SEP> OC <tb> <SEP> , <SEP> deblock <SEP> > <SEP> g <SEP> acylation <SEP> \ <SEP> N <SEP> > <SEP> deblockE <tb> <SEP> HO <SEP> CH2 <SEP> CH2 <SEP> deblOck <tb> <SEP> deblock <SEP> 3' <tb> <SEP> H2 <SEP> CH2 <tb> <SEP> LXXXVII <SEP> i <SEP> NH-CO-R5 <SEP> ss <SEP> LXXXVIII <tb> <SEP> NH-CO-2Ss <SEP> NH-CO-R45 <tb>

Claims: CLAIMS 1. A compound of formula I, EMI95.1 wnerein R1 is (a) hydrogen or (b) a blocking group; wherein R3 is (a) hydrogen (b) alkyl of 1 to 8 carbon atoms, inclusive, (c) -R31-0-R32, wherein R31 is alkylene of 1 to 4 carbon atoms, inclusive, and R32 is hydrogen or alkyl of 1 to 6 carbon atoms, inclusive, with the proviso that the sum of the number of carbon atoms in R31 and the number of carbon atoms in R32 is less than or equal to 7, (d) -R31-NR33R34, wherein R31 is as defined above, wherein R33 is hydrogen or alkyl of 1 to 6 carbon atoms, inclusive, and i4 is hydrogen, alkyl of 1 to 6 carbon atoms, inclusive, or a blocking group, with the proviso that if R34 is not a blocking group, the sum of the number of carbon atoms in R3i and the number of carbon atoms in whichever of R33 or R34 has the larger number of carbon atoms is less than or equal to 7, or (e) alkyl of 1 to 4 carbon atoms, inclusive, substituted with 1, 2, or 3 halogen atoms; wherein A is (a) =N2, (b) a-H:S-H, (c) a-H:ss-X, wherein X is chlorine or bromine, i.e., the configuration at C-3' is (R), (d) &alpha;-Cl: :ss-Cl, (e) =CH(NRsR6), with the proviso that (i) R1 is a blocking group and (ii) R34 is not hydrogen and, if R33 is hydrogen, R34 is a blocking group, and wherein q and t , being the same or different, are alkyl of 1 to 6 carbon atoms, inclusive, and wherein the configuration at the vinylogous carbon bonded to C-3' is, with respect to C-2', E or Z, but not both, (f) a-CHO: :ss-H, i.e., the configuration at C-3' is (R), with the proviso that (i) R1 is a blocking group and (ii) R34 is not hydrogen and, if R33 is hydrogen, R34 is a blocking group, (g) methylene (=CH2), with the proviso that (i) R1 is a blocking group and (ii) R34 is not hydrogen and, if 3 is hydrogen, R34 is a blocking group, (h) a-CH20H:ss-H, i.e., the configuration at C-3' is (R), (i) &alpha;-H:ss-CH2NR2R6 or &alpha;-CH2NR5R6:ss-H, i.e.. the configuration at C-3' is (R) or (S) but not both, (j) &alpha;-CH2OH: :ss-OH, i.e., the configuration at C-3' is (S), (k) epoxymethano (-O-CH2- or -CH2-O-), with the proviso that (i) R1 is a blocking group and (ii) R34 is not hydrogen and, if 3 is hydrogen, R34 is a blocking group, (1) &alpha;-OH:ss-CH2N3 or a-CH2N3:ss-OH, i.e., the configuration at C-3' is (R) or (S), with the proviso that (i) R1 is a blocking group and (ii) R34 is not hydrogen and, if 3 is hydrogen, R34 is a blocking group, (m) a-OH:ss-(CH2)m-CN or a-(CH2)m-CN:ss-OH, wherein m is O or 1, i.e., the configuration at C-3' is (R) or (S), (n) &alpha;-OH: :ss-(CH2)p-NR41R42 or a-(Ci )p-NR1 Wz 8 -OH, wherein p is 1 or 2, and R41 and R42, being the same or different, are (i) hydrogen (ii) alkyl of 1 to 12 carbon atoms, inclusive, (iii) aryl of 6 to 12 carbon atoms, (iv) aralkyl of 7 to 12 carbon atoms, inclusive, optionally substituted by one or two (1) fluoro, chloro or iodo, (2) -NR46R47, wherein R46 and R47 are hydrogen or alkyl of one to 6 carbon atoms, inclusive, being the same or different, (3) cyano, (4) hydroxy, (5) carboxy, (6) alkoxycarbonyl of 2 to 5 carbon atoms, inclusive, or (7) alkoxy of one to 4 carbon atoms, inclusive, (v) -R43-R44, wherein -R43- is a single bond or 43 is alkylene of 1 to 4 carbon atoms, inclusive, and R44 is cycloalkyl of 3 to 10 carbon atoms, inclusive, or R41 and R42 taken together with N form a heterocyclic amine ring with 3 to 10 carbon atoms, inclusive, in the ring, or (vi) -CO-R45, wherein R45 is (a) alkyl of one to 12 carbon atoms, inclusive, or aryl or aralkyl of 7 to 12 carbon atoms optionally substituted by one or two (1) fluoro, chloro or iodo, (2) -NR46R47, wherein R46 and 7 are hydrogen or alkyl of one to 6 carbon atoms, inclusive, being the same or different, (3) cyano, (4) hydroxy, (5) carboxy, (6) alkoxycarbonyl of 2 to 5 carbon atoms, inclusive, or (7) alkoxy of one to 4 carbon atoms, inclusive, (b) -R43-R44 wherein R43 and 4 are as defined above, or (c) pyridyl, piperazyl, pyrollyl or morpholinyl optionally substituted by (1) fluoro, chloro or iodo, (2) -NR46R47, wherein R46 and 7 are hydrogen or alkyl of one to 6 carbon atoms, inclusive, being the same or different, (3) cyano, (4) hydroxy, (5) carboxy, (6) alkoxycarbonyl of 2 to 5 carbon atoms, inclusive, or (7) alkoxy of one to 4 carbon atoms, inclusive; and wherein B1 is a-OH:ss-H and B2 is oxo, when A is =l or =CH(NR5R6), or B1 is &alpha;-B3:ss-H and Bz is &alpha;-B,4 ss 8 -OH wherein B and 8 are taken together to form oxa (-0-), when A is not = or =CH(Ng or the pharmacologically acceptable acid addition salts thereof when R1 and R34 are not blocking groups and A is not =N2. 2. A compound according to claim 1 selected from the group consisting of: 3'-chloro-3'-doxo-N,N'-di-tert-butoxycarbonyl spectinomycin; 3'-bromo-3'-3'-doxo-N,N'-di-tert-butoxycarbonyl spctinomycin; 3l-deoxo-N,N'-di-tert-butoxycarbonyl-3',3'-dichlorospectinomycin; 3'-chloro-3'-deoxospectinomycin dihydrochloride; 3'-bromo-3'-deoxospectinomycin dihydrochloride; 3',3'-dichloro-3'-doxospectinomycin dihydrochloride; 3'-(dimethylamino)methylene-N,N'-dicarbobenzyloxy-seco-spectino- mycin; N,N'-dicarbobenzyloxy-3'-deoxo-3'-formylspectinomycin; N,N'-dicarbobenzyloxy-3'-deoxo-3'-(hydroxymethyl)-spectinomycin; 3'-deoxo-3'-(hydroxymethyl)spectinomycin; N,N'-dicarbobenzyloxy-3'-deoxo-3'-methylenespectinomycin; N,N'-dibenzyloxycarbonyl-3'-deoxo-3'-(N,N-dimethylaminomethyl)dihydrospectinomycin; ; N,N'-dicarbobenzyloxy-3'-(hydroxymethyl)dShydrospectinomycin; 3'-(hydroxymethyl)dihydrospectinomycin dihydrochloride; N,N'-dibenzyloxycarbonyl-3'-deoxo-3'-(N,N'-dimethylaminomethyl) specti nomycin; 3'-deoxo-3'-(N,N-dimethylaminomethyl)spectinomycin trihydrochloride; N,N'-dibenzyloxycarbonyl-3'-deoxo-3'-methylene-spectinomycin oxide; N,N'-dibenzyloxycarbonyl-3'-azidomethyidShydrospectinomycin; 3-S-3'-aminometghyldihydrospectinomycin trihydrochloride; N,N'-dibenzyloxycarbonyl-3'-(cyanomethyl)dShydro-spectinomycin; 3'-(cyanomethyl)dihydrospectinomycin dihydrochloride; N,N'-dibenzyloxycarbonyl-3-(S)-3'-aminomethyidShydro-spectino- mycin; ; N,N'-dibenzyloxyCarbonyl-3'-(R)-3'-aminomethyidshydro¯spectino- mycin; N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N-ethylamino-methyl)dihydrospectinomycin; N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N-octylamino-methyl)dihydrospectinomycin; 3'-(R)-34-(N-ethylaminometnyl)dShydrospectinomycin trihydrocnloride; 3'-(R)-3'-(N-octylaminomethyl)dShydrospectinomycin trihydrochloride; N,N'-dibenzyloxycarbonyl-3'-(S)-3'-(N-ethylaminomethyl)-dihydro specti namyci n; 3'-(S)-3'-(N-ethylaminomethyl)dihydrospectinomycin trihydrochloride; N,N'-dibenzyloxycarbonyl-3'-(S)-3'-(N-butylamino-methyl)dihydrospectinomycin; 3'-(S)-3'-(N-butylaminomethyl)dShydrospectinomycin trihydrochloride; N,N'-dibenzyloxycarbonyl-3'-(S)-3'-(N-octylamino-methyl)dihydrospectinomycin; ; 3'-(S)-3'-(N-octylaminomethyl)dihydrospectinomycin trihydrochloride; 3'-(R)-3'-aminomethyldihydrospectinomycin trihydrochloride; 3'-(S)-3'-(n-propylaminomethyl)-3'-dihydrospectinomycin tri hydrocnloride; 3'-R-3'[(3-dimethylaminopropyl)-aminomethyl]-dihydrospectinomycin tetrahydrochl ori de; N,N'-dicarbobenzyloxy-3'-(R)-3'-(n-butylaminomethyl)-3'-di- hydrospectinomycin; 3-(R)-3'-(n-butylaminomethyl)-3'-dShydrospectinomycin trihydrochloride; N,N'-dibenzyloxycarbonyl-3'-(S)-3'-(aminomethyl)-dihydrospec- tinomycin; N,N'-dibenzyloxycarbonyl-3' -(R)-spectinomycin cyanohydrin; N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(aminomethyl)-dihydrospectino- mycin; ; N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N-hexylamino-methyl)-dihydrospectinomycin; N,N'-dicarbobenzyloxy-3'-(N,N-dihexylamino-methyl)-dihydro- spectinomycin; N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N-isobutylamino-methyl)- dihydrospectinomycin; 3'-(N,N-diisobutylaminomethyl)-dihydrospectinomycin; N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N-cyclohexyimethyl-arnno- methyl) -di hydrospecti nomyci n; N,N'-dibenzyloxycarbonyl-3'-(R)-3'-rN,N-di(cycloheXylmethyl)- amino-methyl]-dihydrospectinomycin; 3'-(R)-3'-(N-hexylaminomethyl )-dihydrospectinomycin trihydro cnloride; 3'-(R)-3'-(N-isobutylaminomethyl )-dihydrospectinomycin trihydrochloride; ; 3'-(R)-3'-(N-cyclohexylmethylaminomethyl )-dihydrospectinomycin tri hydrochloride; 3'-(R)-3'-(N,N-dihexylaminomethyl)-dihydrospectinomycin trihydrochloride; 3'-(R)-3'-(N,N-diisobutylaminomethyl)-dihydrospectinomycin trihydrochloride; 3'-(R)-3'-(N,N-di[cyclohexylmethyl]aminomethyl)dihydro-spectinomycin trihydrochloride; N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(cyclopentylaminomethyl)- dihydrospectinomycin; N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(cyclohexylaminomethyl3- dihydrospectinomycin; N,N'-dibenzyloxycarbonyl-3'-tR)-3'-(cycloheptylaminomethyl)- dihydrospectinomycin; 3'-(R)-3'-(cyclopentylaminomethyl)dShydrospectinomycin trihydrochloride; 3'-(R)-3'-(cyclohexylaminomethyl)dihydrospectinomycin trihydrochloride; ; 3l-(R)-3'-(cycloheptylaminomethyl)dShydrospectinomycin trihydro chloride; N,N'-dibenzyloxycarbonyl-3'-(R)-3' r( 2-hydroxyethyl)amino- methyl]dihydrospectinomycin; N,N'-dibenzyloxycarbonyl-3'-(R)-3'-[(5-hydroxylpentyl)aminomethyl]dihydrospectinomycin; N,N'-dibenzyloxycarbonyl-3'-(R)-3'- t6-chloroheXyl)amino¯ methyl]dihydrospectinomycin; N,N'-dicarbobenzyloxy-3'-(R)-3'-[carbomethoxymethyl)aminomethyl]dihydrospectinomycin; 3'-(R)-3'-[(2-hydroxyethyl)aminoimethyl]dihydrospectinomycin trihydrochloride; 3'-(R)-3'-[(5-hydroxypentyl)aminomethylidShydrospectinomycin trihydrochloride; 3'-(R)-3'-[(6-chlorohexyl)aminomethylndShydrospectinomycin tri hydrochloride; 3'-(R)-3'-[(carbomethoxymethyl)aminomethyl]dihydrospetinomycin trihydrochloride; ; N,N'-dibenzyloxycarbonyl-3'-(R)-3'-[(benzyloxyCarbonyl methyl )aminomethyl] dihydrospectinomycin; 3'-(R)-3'-[(carboxymethyl)aminomethyl]dihydrospectinomycin trihydrochloride; N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N-acetylaminomethyl) dihydrospectinomycin; 3'-(R)-3'-(acetylaminomethyl)-dShydrospectinomycin dihydrochloride; 3'-(R)-3'-[N-glycylaminomethyl]-dShydrospectinomycin trihydrochloride; 3'-(R)-3'-[N-(pyrolle-2-carbonyl)aminomethyl]-dihydrospectinomycin dihydrochloride; N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(succinylaminomethyl) dihydrospectinomycin; 3'-(R)-3'-(succinylaminomethyl)dihydrospectinomycin trihydrochloride; N,N'-di-benzyloxycarbonyl-3'-(S)-3'-(Nethylaminomethyl) dihydrospectinomycin; N,N'-di-benzyloxycarbonyl-3'-(S)-3'-(N-butylaminomethyl) dihydrospectinomycin; ; N,N'-di-benzyloxycarbonyl-3'-(S)-3'-(N-octylaminomethyl) dihydrospectinomycin; 3'-(S)-3'-(N-ethylaminomethyl) dihydrospectinomycintrihydrochloride; 3'-(S)-3'-(N-butylaminomethyl) dihydrospectinomycintrihydrochloride; 3'-(5)-3'-(N-octylaminomethyl) dihydrospectinomycintrihydrochloride; N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N-ethylaminomethyl) dihydrospectinomycin; N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N-propylaminomethyl) dihydrospectinomycin; N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N-pentylaminomethyl) di hydrospecti nomyci n; N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N-hexylaminomethyl) dihydrospectinomycin; N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N-octylaminomethyl ) dihydrospectinomycin; N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N-isobutylaminomethyl )dihydrospectinomycin; ; N,N'-dimethyloxycarbonyl-3'-(R)-3'-[N-(2-methylbutyl)aminomethyl] di hydrospecti nomyci n; N,N'-dibenzyloxycarbonyl-3'-(R)-3'-[N-cyclohexylmethyl)amino methyl]dihydrospectinomycin; N,N'-dibenzyloxycarbonyl-3'-(R)-3'-[N-cyclooctylmethyl)aminomethyl]dihydrospectinomycin; N,N'-dibenzyloxycarbonyl-3'-(R)-3'-[N,N-(dicyclohexylmethyl) aminomethyl di hydrospecti nomyci n; N,N'-dibenzyloxycarbonyl-3'-(R)-3'-(N,N-diisobutylaminomethyl ) dihydrospectinomycin; 3'-(R)-3'-(N-ethyl-aminomethyl) dihydrospectinomycin trihydrochloride; 3'-(R)-3'-(N-propyl-aminomethyl) dihydrospectinomycin trihydrochloride; 3'-(R)-3'-(N-pentyl-aminomethyl) dihydrospectinomycin trihydrochloride; 3'-(R)-3'-(N-hexyl-aminomethyl) dihydrospectinomycin trihydrochloride; ; 3'-(R)-3'-(N-octyl-aminomethyl) dihydrospectinomycin trihydro chloride; 3'-(R)-3'-(N-isobutylaminomethyl) dihydrospectinomycin trihydrochloride; 3'-(R)-3'-[N-(2-methylbutyl)aminomethylidShydrospectinomycin trihydrochloride; 3'-(R)-3'-[N-(cyclohexylmethyl)aminomethylidShydrospectinomycin tri hydrochloride; 3'-(R)-3'-[N-(cyclooctylmethyl)aminomethylidihydrospectinomycin trihydrochloride; 3'-(R)-3'-(N,N-dihexylaminomethyl)dihydrospectinomycin trinydrochloride; 3'-(R)-3'-[N,N-(dicyclohexylmethyl)aminomethylldShydro- spectinomycin trihydrochloride; and 3'-(R)-3'-(N,N-diisobutylaminomeXnyl)dihydrospectinomycin tri hydrochloride. 3. A process for preparing a compound of formula II EMI103.1 wherein R1 and R3 are as defined in claim 1, which comprises: reacting in an inert organic solvent a compound of formula III EMI103.2 wherein R4 is an aryl group, with an organic amine base. 4. A process for preparing a compound of formula IV, EMI104.1 wherein R7 is a blocking group; wherein R3 is as defined in claim 1; wherein R5 and R6, being the same or different, are alkyl of 1 to 6 carbon atoms, inclusive; and wherein the configuration at the carbon atom to wnicn -NR5R5 is bonded is, with respect to C-2', E or Z but not both, which comprises: recting a ompound of formula V EMI104.2 wherein R7 is as defined in claim 1, with a compound of formula VI + CM 2=NR 5R 6X6 wherein X6 is chlorine or bromine, in the presence of a tertiary amine base in a solvent R8CN, wherein R8 is alkyl of 1 to 3 carbon atoms, inclusive. 5. A process for C-3' stereoselectively preparing a compound of formula VII EMI105.1 wherein R1 and R3 are as defined in claim 1, which comprises reacting a compound of formula VIII EMI105.2 wherein R1 and R3 are as defined above, with a compound which is a source of cyano groups, in an inert organic solvent in the presence of base or basic ion-exchange resin, and allowing the reaction product to remain in solution for a length of time sufficient to result in the formation of an epimeric mixture containing an amount of the compound of formula VII greater than the amount of its C-3' epimer. 6. A process for C-3' stereoselectively preparing a compound of formula X EMI105.3 wherein R1 and R3 are as defined in claim 1, which comprises reacting a compound of formula VIII as defined in claim 5 with a compound which is a source of cyano groups, in an inert organic solvent in the presence of base or basic ion-exchange resin, and terminating the reaction prior to the formation of an epimeric mixture containing an amount of C-3' epimer greater than the amount of the compound of formula X, either by quenching the reaction by the addition of acid to neutralise the base or basic ion-exchange resin or, if no other base is present, removing the resin. 7. A process for preparing a compound of formula VII as defined in claim 5, which comprises reacting a compound of formula X as defined in claim 6 with a base or a basic ion-exchange resin in an inert organic solvent.

Inventors: FRITZEN, EDWARD LAWRENCE, THOMAS, RICHARD CHARLES
Applicants: THE UPJOHN COMPANY
Application year: 1982
Main classification: C07D493
IPC codes: C07H15, A61K31, A61P31, C07D493, C07D309