Spectinomycin analogs and methods for the preparation thereof

Claim 2

Anomers and asteric mixtures of a compound having the formula ##STR214## wherein R is selected from the group consisting of ##STR215## wherein R 1 through R 4 may be the same or different and are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, lower haloalkyl, lower aminoalkyl, lower alkynyl, --OX and --(CH 2 ) n --OX and isomers thereof with the proviso that R 1 and R 2 are not hydroxy and one of R 3 and R 4 must be hydrogen, wherein X is selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, benzyl and acyl; n is an integer of from one to four, R 5 is hydrogen or lower alkyl; R 6 through R 14 are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl and lower alkynyl with the proviso that one of R 7 and R 8 is always hydrogen and one of R 11 and R 12 is always hydrogen, and B and B 1 are the same or different and are selected from the group consisting of hydrogen, hydroxy, alkoxy, o-lower alkenyl, thio, thio-lower alkyl and thio-lower alkenyl, and A is selected from the group consisting of oxygen and sulfur, hydrated forms thereof, and pharmaceutically acceptable salts of the compound of formula I and hydrated forms thereof; with the proviso that when the compound has the formula ##STR216## B 1 cannot be hydroxy.

Claim 3

A compound of claim 1 having the formula ##STR217## wherein R 1 through R 14 , A, B and B 1 are the same as in claim 1, with the proviso that when R 1 and R 2 are both --(CH 2 ) n --OX and X is acyl, R 3 and R 4 are hydrogen.

Claim 4

A compound of claim 2 having the formula ##STR218## wherein R 8 and R 12 are lower alkyl; B and B 1 are selected from the group consisting of hydroxy and lower alkoxy.

Claim 5

A compound according to claim 3, 5'-desmethylspectinomycin.

Claim 6

A compound according to claim 2 having the formula ##STR219## wherein R 2 is selected from the group consisting of lower haloalkyl, lower aminoalkyl and --(CH 2 ) n --OH wherein n is an integer of from one to four.

Claim 7

A compound according to claim 5, 6'-hydroxyspectinomycin.

Claim 8

A compound according to claim 5, 6'-chlorospectinomycin.

Claim 9

The dihydrochloride of the compound of claim 7.

Claim 10

A compound according to claim 5, 6'-bromospectinomycin.

Claim 11

The dihydrochloride of the compound of claim 9.

Claim 12

A compound of claim 1 having the formula ##STR220## wherein R 1 through R 14 , A, B and B 1 are the same as in claim 1.

Claim 13

A compound of claim 9 having the formula ##STR221## wherein R 1 , R 8 , and R 12 are lower alkyl, and B and B 1 are selected from the group consisting of hydroxy and alkoxy.

Claim 14

A compound according to claim 12, 4',5'-didehydrospectinomycin.

Claim 15

The dihydrochloride salt of the compound of claim 13.

Claim 16

A process for preparing a compound having the formula ##STR222## which comprises (a) coupling a compound having the formula ##STR223## with a sugar to prepare an oxime; (b) deoximation of the oxime prepared in step (a) to form a cyclic hemiketal and reacting the hemiketal with a base system to form a compound having the formula ##STR224## (c) deprotecting the compound prepared in step (b) to prepare the compound of Formula Ib; wherein R 1 through R 4 may be the same or different and are selected from the group consisting of hydrogen, lower alkyl, lower haloalkyl, lower aminoalkyl, lower alkenyl, lower alkynyl, --OX and --(CH 2 ) n --OX and isomers thereof with the proviso that R 1 and R 2 are not hydroxy and one of R 3 or R 4 must be hydrogen, wherein X is selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, lower alkynyl, benzyl and acyl; n is an integer of from one to four; R 5 is hydrogen or lower alkyl, R 6 through R 14 are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl and lower alkynyl; R 5 is hydrogen or lower alkyl, R' 7 , R' 8 , R' 11 and R' 12 are selected from the group consisting of lower alkyl, lower alkenyl, lower alkynyl, and a blocking group selected from the group consisting of aralkoxycarbonyl, halogenated-alkoxycarbonyl and alkoxycarbonyl; with the proviso that one of R 7 and R 8 is always hydrogen and one of R 11 and R 12 is always hydrogen; and the further proviso that one of R' 7 and R' 8 is always a blocking group and one of R' 11 and R' 12 is always a blocking group; R 15 is acyl; A is selected from the group consisting of oxygen and sulfur; and B and B 1 are the same or different and are selected from the group consisting of hydrogen, hydroxy, alkoxy, o-lower alkenyl, thio, thio-lower alkyl and thio-lower alkenyl.

Claim 17

A process for preparing a compound having the formula ##STR222## which comprises (a) coupling a compound having the formula ##STR223## with a sugar to prepare an oxime; (b) deoximation of the oxime prepared in step (a) to form a cyclic hemiketal and reacting the hemiketal with a base system to form a compound having the formula ##STR224## (c) deprotecting the compound prepared in step (b) to prepare the compound of Formula Ib; wherein R 1 through R 4 may be the same or different and are selected from the group consisting of hydrogen, lower alkyl, lower haloalkyl, lower aminoalkyl, lower alkenyl, lower alkynyl, --OX and --(CH 2 ) n --OX and isomers thereof with the proviso that R 1 and R 2 are not hydroxy and one of R 3 or R 4 must be hydrogen, wherein X is selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, lower alkynyl, benzyl and acyl; n is an integer of from one to four; R 5 is hydrogen or lower alkyl, R 6 through R 14 are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl and lower alkynyl; R 5 is hydrogen or lower alkyl, R' 7 , R' 8 , R' 11 and R' 12 are selected from the group consisting of lower alkyl, lower alkenyl, lower alkynyl, and a blocking group selected from the group consisting of aralkoxycarbonyl, halogenated-alkoxycarbonyl and alkoxycarbonyl; with the proviso that one of R 7 and R 8 is always hydrogen and one of R 11 and R 12 is always hydrogen; and the further proviso that one of R' 7 and R' 8 is always a blocking group and one of R' 11 and R' 12 is always a blocking group; R 15 is acyl; A is selected from the group consisting of oxygen and sulfur; and B and B 1 are the same or different and are selected from the group consisting of hydrogen, hydroxy, alkoxy, o-lower alkenyl, thio, thio-lower alkyl and thio-lower alkenyl.

Claim 18

A process according to claim 15 wherein the compound prepared has the formula ##STR225## wherein R' 8 and R' 12 are lower alkyl; and B' and B' 1 are selected from the group consisting of hydroxy and lower alkoxy.

Claim 19

A process according to claim 15 wherein the compound prepared is 5'-dimethylspectinomycin.

Claim 20

A process for preparing a compound having the formula ##STR226## which comprises (a) coupling a compound having the formula ##STR227## with a sugar to prepare an oxime; (b) deoximating the oxime prepared in step (a) to form a cyclic hemiketal and reacting the hemiketal with a base system to prepare a compound having the formula ##STR228## and (c) deprotecting the compound prepared in step (b); wherein R 1 through R 4 may be the same or different and are selected from the group consisting of hydrogen, lower alkyl, lower haloalkyl, lower aminoalkyl, lower alkenyl, lower alkynyl, --OX and --(CH 2 ) n --OX and isomers thereof with the proviso that R 1 and R 2 are not hydroxy and one of R 3 or R 4 must be hydrogen; wherein X is selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, lower alkynyl, benzyl and acyl; n is an integer of from one to four; R 5 is hydrogen or lower alkyl, R 6 through R 14 are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl and lower alkynyl; R 5 is hydrogen or lower alkyl, R' 7 , R' 8 , R' 11 and R' 12 are selected from the group consisting of lower alkyl, lower alkenyl, lower alkynyl, and a blocking group selected from the group consisting of aralkoxycarbonyl, halogenated-alkoxycarbonyl and alkoxycarbonyl; with the proviso that one of R 7 and R 8 is always hydrogen and one of R 11 and R 12 is always hydrogen; and the further proviso that one of R' 7 and R' 8 is always a blocking group and one of R' 11 and R' 12 is always a blocking group; R 16 is lower alkyl, aralkyl or aroyl; A is selected from the group consisting of oxygen and sulfur; and B and B 1 are the same or different and are selected from the group consisting of hydrogen, hydroxy, alkoxy, o-lower alkenyl, thio, thio-lower alkyl and thio-lower alkenyl.

Claim 21

A process for preparing a compound having the formula ##STR226## which comprises (a) coupling a compound having the formula ##STR227## with a sugar to prepare an oxime; (b) deoximating the oxime prepared in step (a) to form a cyclic hemiketal and reacting the hemiketal with a base system to prepare a compound having the formula ##STR228## and (c) deprotecting the compound prepared in step (b); wherein R 1 through R 4 may be the same or different and are selected from the group consisting of hydrogen, lower alkyl, lower haloalkyl, lower aminoalkyl, lower alkenyl, lower alkynyl, --OX and --(CH 2 ) n --OX and isomers thereof with the proviso that R 1 and R 2 are not hydroxy and one of R 3 or R 4 must be hydrogen; wherein X is selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, lower alkynyl, benzyl and acyl; n is an integer of from one to four; R 5 is hydrogen or lower alkyl, R 6 through R 14 are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl and lower alkynyl; R 5 is hydrogen or lower alkyl, R' 7 , R' 8 , R' 11 and R' 12 are selected from the group consisting of lower alkyl, lower alkenyl, lower alkynyl, and a blocking group selected from the group consisting of aralkoxycarbonyl, halogenated-alkoxycarbonyl and alkoxycarbonyl; with the proviso that one of R 7 and R 8 is always hydrogen and one of R 11 and R 12 is always hydrogen; and the further proviso that one of R' 7 and R' 8 is always a blocking group and one of R' 11 and R' 12 is always a blocking group; R 16 is lower alkyl, aralkyl or aroyl; A is selected from the group consisting of oxygen and sulfur; and B and B 1 are the same or different and are selected from the group consisting of hydrogen, hydroxy, alkoxy, o-lower alkenyl, thio, thio-lower alkyl and thio-lower alkenyl.

Claim 22

A process according to claim 18 wherein the compound prepared is 6'-hydroxyspectinomycin.

Claim 23

A process according to claim 18 wherein the compound prepared is 6'-chlorospectinomycin.

Claim 24

A process according to claim 18 wherein the compound prepared is 6'-bromospectinomycin.

Claim 25

A process for preparing a compound having the formula ##STR229## which comprises (a) coupling a compound having the formula ##STR230## with a sugar to prepare an oxime; (b) deoxinating the oxime prepared in step (a) to form a cyclic hemiketal; (c) reacting the hemiketal with a base system; (d) hydrolysis of the product formed in step (c) in the presence of a base to prepare a compound having the formula ##STR231## and (e) deprotecting the compound prepared in step (e); wherein R 1 is selected from the group consisting of hydrogen, lower alkyl, lower haloalkyl, lower aminoalkyl, lower alkenyl, lower alkynyl, --OX and --(CH 2 ) n --OX and isomers thereof with the proviso that R 1 is not hydroxy; wherein X is selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, lower alkynyl, benzyl and acyl; n is an integer of from one to four; R 5 is hydrogen or lower alkyl, R 6 through R 14 are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl and lower alkynyl; R 5 is hydrogen or lower alkyl; R' 7 , R' 8 , R' 11 and R' 12 are selected from the group consisting of lower alkyl, lower alkenyl, lower alkynyl, and a blocking group selected from the group consisting of aralkoxycarbonyl, halogenated-alkoxycarbonyl and alkoxycarbonyl; with the proviso that one of R 7 and R 8 is always hydrogen and one of R 11 and R 12 is always hydrogen; and the further proviso that one of R' 7 and R' 8 is always a blocking group and one of R' 11 and R' 12 is always a blocking group; R 15 is acyl; A is selected from the group consisting of oxygen and sulfur; and B and B 1 are the same or different and are selected from the group consisting of hydrogen, hydroxy, alkoxy, o-lower alkenyl, thio, thio-lower alkyl and thio-lower alkenyl.

Claim 26

A process for preparing a compound having the formula ##STR229## which comprises (a) coupling a compound having the formula ##STR230## with a sugar to prepare an oxime; (b) deoxinating the oxime prepared in step (a) to form a cyclic hemiketal; (c) reacting the hemiketal with a base system; (d) hydrolysis of the product formed in step (c) in the presence of a base to prepare a compound having the formula ##STR231## and (e) deprotecting the compound prepared in step (e); wherein R 1 is selected from the group consisting of hydrogen, lower alkyl, lower haloalkyl, lower aminoalkyl, lower alkenyl, lower alkynyl, --OX and --(CH 2 ) n --OX and isomers thereof with the proviso that R 1 is not hydroxy; wherein X is selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, lower alkynyl, benzyl and acyl; n is an integer of from one to four; R 5 is hydrogen or lower alkyl, R 6 through R 14 are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl and lower alkynyl; R 5 is hydrogen or lower alkyl; R' 7 , R' 8 , R' 11 and R' 12 are selected from the group consisting of lower alkyl, lower alkenyl, lower alkynyl, and a blocking group selected from the group consisting of aralkoxycarbonyl, halogenated-alkoxycarbonyl and alkoxycarbonyl; with the proviso that one of R 7 and R 8 is always hydrogen and one of R 11 and R 12 is always hydrogen; and the further proviso that one of R' 7 and R' 8 is always a blocking group and one of R' 11 and R' 12 is always a blocking group; R 15 is acyl; A is selected from the group consisting of oxygen and sulfur; and B and B 1 are the same or different and are selected from the group consisting of hydrogen, hydroxy, alkoxy, o-lower alkenyl, thio, thio-lower alkyl and thio-lower alkenyl.

Claim 27

A process according to claim 22 wherein the compound prepared has the formula ##STR232## wherein R 1 , R 8 , and R 12 are lower alkyl and B and B are selected from the group consisting of hydroxy and alkoxy.

Claim 28

A process according to claim 23 wherein the compound prepared is 4',5'-didehydrospectinomycin.

Claim 29

Anomers and asteric mixtures of a compound having the formula ##STR233## wherein R is selected from the group consisting of ##STR234## wherein R 1 through R 4 may be the same or different and are selected from the group consisting of hydrogen, lower alkyl, lower haloalkyl, lower aminoalkyl, lower alkenyl, lower alkynyl, --OX and --(CH 2 ) n --OX and isomers thereof, with the proviso that R 1 and R 2 are not hydroxy and one of R 3 and R 4 must be hydrogen, wherein X is selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, lower alkynyl, benzyl and acyl; n is an integer of from one to four, with the proviso that when one of R 1 through R 4 is --(CH 2 ) n --OX and X is acyl, the others are hydrogen; R 5 is hydrogen or lower alkyl; wherein R 6 , R 9 , R 10 , R 13 and R 14 are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, and lower alkynyl; R 5 is hydrogen or lower alkyl; R' 7 , R' 8 , R' 11 and R' 12 are selected from the group consisting of lower alkyl, lower alkenyl, lower alkynyl, and a blocking group selected from the group consisting of aralkoxycarbonyl, halogenatedalkoxy carbonyl and alkoxycarbonyl; with the proviso that one of R' 7 and R' 8 is always a blocking group and one of R' 11 and R' 12 is always a blocking group; R 15 is hydrogen or acyl; A is selected from the group consisting of oxygen and sulfur, and B and B are selected from the group consisting of hydrogen, hydroxy, alkoxy, o-lower alkenyl, thio, thio-lower alkyl and thio-lower alkenyl; with the proviso that when the compound has the formula ##STR235## wherein CBz is carbobenzyloxy, B 1 cannot be hydrogen or hydroxy.

Claim 30

Anomers and asteric mixtures of a compound having the formula ##STR233## wherein R is selected from the group consisting of ##STR234## wherein R 1 through R 4 may be the same or different and are selected from the group consisting of hydrogen, lower alkyl, lower haloalkyl, lower aminoalkyl, lower alkenyl, lower alkynyl, --OX and --(CH 2 ) n --OX and isomers thereof, with the proviso that R 1 and R 2 are not hydroxy and one of R 3 and R 4 must be hydrogen, wherein X is selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, lower alkynyl, benzyl and acyl; n is an integer of from one to four, with the proviso that when one of R 1 through R 4 is --(CH 2 ) n --OX and X is acyl, the others are hydrogen; R 5 is hydrogen or lower alkyl; wherein R 6 , R 9 , R 10 , R 13 and R 14 are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, and lower alkynyl; R 5 is hydrogen or lower alkyl; R' 7 , R' 8 , R' 11 and R' 12 are selected from the group consisting of lower alkyl, lower alkenyl, lower alkynyl, and a blocking group selected from the group consisting of aralkoxycarbonyl, halogenatedalkoxy carbonyl and alkoxycarbonyl; with the proviso that one of R' 7 and R' 8 is always a blocking group and one of R' 11 and R' 12 is always a blocking group; R 15 is hydrogen or acyl; A is selected from the group consisting of oxygen and sulfur, and B and B are selected from the group consisting of hydrogen, hydroxy, alkoxy, o-lower alkenyl, thio, thio-lower alkyl and thio-lower alkenyl; with the proviso that when the compound has the formula ##STR235## wherein CBz is carbobenzyloxy, B 1 cannot be hydrogen or hydroxy.

Claim 31

A compound of claim 25 having the formula ##STR236## wherein R 1 through R 4 , R 6 , R' 7 , R' 8 , R 9 , R 10 , R' 11 , R' 12 , R 13 , R 14 , A, B and B 1 are the same as in claim 25.

Claim 32

A compound of claim 26 having the formula ##STR237## wherein R' 8 and R' 12 are lower alkyl, B and B 1 are hydrogen or lower alkoxy and CBz is carbobenzyloxy.

Claim 33

A compound according to claim 27, N,N'-di-carbobenzyloxy-5-desmethylspectinomycin.

Claim 34

A compound according to claim 26 having the formula ##STR238## wherein R is selected from the group consisting of lower haloalkyl, lower aminoalkyl and --(CH 2 ) n --OH wherein n is an integer of from one to four.

Claim 35

A compound according to claim 26, N,N'-dicarbobenzyloxy-6'-hydroxyspectinomycin.

Claim 36

A compound according to claim 26, N,N'-dicarbobenzyloxy-6'-chlorospectinomycin.

Claim 37

A compound according to claim 26, N,N'-dicarbobenzyloxy-6'-bromospectinomycin.

Claim 38

A compound of claim 25 having the formula ##STR239## wherein R 1 , R 6 , R' 7 , R' 8 , R 9 , R 10 , R' 11 , R' 12 , R 13 , R 14 , A, B and B 1 are the same as in claim 25.

Claim 39

A compound according to claim 33 wherein R 15 is hydrogen.

Claim 40

A compound of claim 34 having the formula ##STR240## wherein R 1 , R' 8 and R' 12 are lower alkyl, A is oxygen or sulfur, and B and B 1 are selected from the group consisting of hydroxy and alkoxy.

Claim 41

A compound according to claim 35 having the formula ##STR241##

Claim 42

A compound according to claim 33 wherein R 15 is acyl.

Claim 43

A compound according to claim 37 having the formula ##STR242## wherein R', R' 8 , and R' 12 are lower alkyl, B and B 1 are hydroxy or alkoxy and Ac is acyl.

Claim 44

A compound according to claim 38, N,N'-dicarbobenzyloxy-2'-O-acetyl-4'-,5'-didehydrospectinomycin.

Claim 45

Anomers and asteric mixtures of a compound having the formula ##STR243## wherein R 1 through R 3 may be the same or different and are selected from the group consisting of hydrogen, lower alkyl, lower haloalkyl, lower aminoalkyl, lower alkenyl, lower alkynyl, --OX and --(CH 2 ) n --OX and isomers thereof with the proviso that R 1 , R 2 and R 3 are not hydroxy, wherein X is selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, lower alkynyl, benzyl and acyl; n is an integer of from one to four, R 5 is hydrogen or lower alkyl; wherein R 6 , R 9 , R 10 , R 13 and R 14 are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl and lower alkynyl; R 5 is hydrogen or lower alkyl; R' 7 , R' 8 , R' 11 and R' 12 are selected from the group consisting of lower alkyl, lower alkenyl, lower alkynyl, and a blocking group selected from the group consisting of aralkoxycarbonyl, halogenated alkoxycarbonyl and alkoxycarbonyl; with the proviso that one of R' 7 and R' 8 is always a blocking group and one of R' 11 and R' 12 is always a blocking group; R 16 is lower alkyl, aralkyl or aroyl; A is selected from the group consisting of oxygen and sulfur, and B and B 1 are the same or different and are selected from the group consisting of hydrogen, hydroxy, alkoxy, o-lower alkenyl, thio, thio-lower alkyl and thio-lower alkenyl.

Claim 46

Anomers and asteric mixtures of a compound having the formula ##STR243## wherein R 1 through R 3 may be the same or different and are selected from the group consisting of hydrogen, lower alkyl, lower haloalkyl, lower aminoalkyl, lower alkenyl, lower alkynyl, --OX and --(CH 2 ) n --OX and isomers thereof with the proviso that R 1 , R 2 and R 3 are not hydroxy, wherein X is selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, lower alkynyl, benzyl and acyl; n is an integer of from one to four, R 5 is hydrogen or lower alkyl; wherein R 6 , R 9 , R 10 , R 13 and R 14 are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl and lower alkynyl; R 5 is hydrogen or lower alkyl; R' 7 , R' 8 , R' 11 and R' 12 are selected from the group consisting of lower alkyl, lower alkenyl, lower alkynyl, and a blocking group selected from the group consisting of aralkoxycarbonyl, halogenated alkoxycarbonyl and alkoxycarbonyl; with the proviso that one of R' 7 and R' 8 is always a blocking group and one of R' 11 and R' 12 is always a blocking group; R 16 is lower alkyl, aralkyl or aroyl; A is selected from the group consisting of oxygen and sulfur, and B and B 1 are the same or different and are selected from the group consisting of hydrogen, hydroxy, alkoxy, o-lower alkenyl, thio, thio-lower alkyl and thio-lower alkenyl.

Claim 47

A compound of claim 40 having the formula ##STR244## wherein R 1 , R 2 , R 3 , R 6 , R 9 , R 10 , R 13 , R 14 , R 16 , R' 7 , R' 8 , R' 11 , R' 12 , B and B 1 are as in claim 40.

Claim 48

A compound of claim 41 having the formula ##STR245## wherein R 16 is lower alkyl and R 1 , R 2 , R 3 , R' 7 , R' 8 , R' 11 , and R' 12 are the same as in claim 41.

Claim 49

A compound of claim 42 having the formula ##STR246## wherein R 1 , R 2 , R 3 and R 16 are as in claim 42 and CBz is carbobenzyloxy.

Claim 50

A compound of claim 43 having the formula ##STR247## wherein R 2 and CBz are the same as in claim 43.

Claim 51

A compound of claim 44 having the formula ##STR248## wherein CBz is carbobenzyloxy.

Claim 52

A process for preparing anomers and asteric mixtures of a compound having the formula ##STR249## which comprises (a) coupling a compound having the formula ##STR250## with a sugar to prepare an oxime; and (b) deoximating the oxime prepared in step (a) to form a cyclic hemiketal and reacting the hemiketal with a base system; wherein R 1 through R 2 may be the same or different and are selected from the group consisting of hydrogen, lower alkyl, lower haloalkyl, lower aminoalkyl, lower alkenyl, lower alkynyl, --OX and --(CH 2 ) n --OX with the proviso that R 1 , R 2 and R 3 are not hydroxy; wherein X is selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, lower alkynyl, benzyl and acyl; n is an integer of from one to four; R 5 is hydrogen or lower alkyl; wherein R 6 , R 9 , R 10 , R 13 and R 14 are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, and lower alkynyl; R' 7 , R' 8 , R' 11 and R' 12 are selected from the group consisting of lower alkyl, lower alkenyl, lower alkynyl, and a blocking group selected from the group consisting of aralkoxycarbonyl, halogenated alkoxy carbonyl and alkoxycarbonyl; with the proviso that one of R' 7 and R' 8 is always a blocking group and one of R' 11 and R' 12 is always a blocking group; R 16 is lower alkyl, aralkyl or aroyl; A is selected from the group consisting of oxygen and sulfur, and B and B 1 are the same or different and are selected from the group consisting of hydrogen, hydroxy, alkoxy, o-lower alkenyl, thio, thio-lower alkyl and thio-lower alkenyl.

Claim 53

A process for preparing anomers and asteric mixtures of a compound having the formula ##STR249## which comprises (a) coupling a compound having the formula ##STR250## with a sugar to prepare an oxime; and (b) deoximating the oxime prepared in step (a) to form a cyclic hemiketal and reacting the hemiketal with a base system; wherein R 1 through R 2 may be the same or different and are selected from the group consisting of hydrogen, lower alkyl, lower haloalkyl, lower aminoalkyl, lower alkenyl, lower alkynyl, --OX and --(CH 2 ) n --OX with the proviso that R 1 , R 2 and R 3 are not hydroxy; wherein X is selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, lower alkynyl, benzyl and acyl; n is an integer of from one to four; R 5 is hydrogen or lower alkyl; wherein R 6 , R 9 , R 10 , R 13 and R 14 are selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, and lower alkynyl; R' 7 , R' 8 , R' 11 and R' 12 are selected from the group consisting of lower alkyl, lower alkenyl, lower alkynyl, and a blocking group selected from the group consisting of aralkoxycarbonyl, halogenated alkoxy carbonyl and alkoxycarbonyl; with the proviso that one of R' 7 and R' 8 is always a blocking group and one of R' 11 and R' 12 is always a blocking group; R 16 is lower alkyl, aralkyl or aroyl; A is selected from the group consisting of oxygen and sulfur, and B and B 1 are the same or different and are selected from the group consisting of hydrogen, hydroxy, alkoxy, o-lower alkenyl, thio, thio-lower alkyl and thio-lower alkenyl.

Claim 54

A process according to claim 46 wherein the compound prepared has the formula ##STR251## wherein R 1 , R 2 , R 3 , R 6 , R' 7 , R' 8 , R 9 , R 10 , R' 11 , R' 12 , R 13 , R 14 , R 16 and B and B 1 are the same as in claim 46.

Claim 55

A process according to claim 47 wherein the compound prepared has the formula ##STR252## wherein R 16 is lower alkyl and R 1 , R 2 , R 3 , R' 7 , R' 8 , R' 11 and R' 12 are as in claim 47.

Claim 56

A process according to claim 48 wherein the compound prepared has the formula ##STR253## wherein R 1 , R 2 , R 3 and R 16 are the same as in claim 48 and CBz is carbobenzyloxy.

Claim 57

A process according to claim 49 wherein the compound prepared has the formula ##STR254## wherein R 2 and CBz are as in claim 49.

Claim 58

A process according to claim 50 wherein the compound has the formula ##STR255## wherein CBz is carbobenzyloxy.

Claim 59

The dihydrochloride of the compound of claim 6.