Process for producing 1,2-trans-glycoside compound
In preparing a glycoside compound from (a) a furanose compound or pyranose compound, and (b) an alcohol compound, a process for preparing a glycoside compound in which glycosidic bond locates selectively trans form relative to C-2 hydroxyl group, the process comprising using a furanose compound wherein the hydroxyl at the 2-position may have a substituent protected with a group A, or a pyranose compound which may have a substituent wherein R 2 and R 3 are the same or different and are each alkyl having 1 to 4 carbon atoms or aryl having or not having a substituent, or R 2 and R 3 are combined to form alkylene having 2 to 4 carbon atoms (the alkylene may be substituted with alkyl having 1 to 4 carbon atoms, or may have intervening phenylene), and m and n are each an integer of 0 or 1.
1. A 2-phosphonoyl-1,2-transglycoside compound of the formula (3) comprising:
Q 1a -O-Q 2 (3)
wherein Q 1a has the following structure:
R 4 , R 5 and R 6 are the same or different and are each a protective group for the saccharide hydroxyl group;
E is methylene or a carbonyl; and
A is
wherein R 2 and R 3 are the same or different and are each an alkyl group having 1 to 4 carbon atoms or an aryl group optionally substituted, or R 2 and R 3 are connected via an alkylene group having 2 to 4 carbon atoms, further wherein the alkylene group is optionally substituted with an alkyl group having 1 to 4 carbon atoms or optionally comprises an intervening phenylene, and m and n are each an integer of 0 or 1;
Q 2 is one of the following groups
wherein L 1 is a group —OA 1 , —OG or —N(J 1 )(J 2 ); G is a protective group for the saccharide hydroxyl, and J 1 and J 2 are each a hydrogen atom or a protective group for the amino; A 1 is
R 2′ and R 3′ are the same or different and are each alkyl comprising 1 to 4 carbon atoms or aryl optionally substituted, or R 2′ and R 3′ are combined with each other to form an alkylene having 2 or 4 carbon atoms, further wherein the alkylene is optionally substituted with alkyl having 1 to 4 carbon atoms, or optionally comprises an intervening phenylene; m′ and n′ are each an integer of 0 or 1;
Z 1 is a group —S—R 1′ , a group —SO—R 1′ , a group —Se—R 1′ , a group —O—C(═NH)CX′ 3 , a halogen atom, an alkoxyl, an alkenyloxy, a group —P(OR 1′ ) 3 , a group —PO(OR 1′ ) 3 or —OG 1 ; R 1′ is an alkyl comprising 1 to 20 carbon atoms, an aryl optionally substituted or a heteroaromatic group; X′ is a halogen atom; G 1 is a protective group for the saccharide hydroxyl;
R 7 , R 8 and R 9 are the same or different and are each a protective group for the saccharide hydroxyl group; and E 1 is methylene or a carbonyl.
2. A 2-phosphonoyl-1,2-transglycoside compound of the formula (3a) comprising:
Q 1a -O-Q 2a (3a)
wherein Q 1a has the following structure:
R 4 , R 5 and R 6 are the same or different and are each a protective group for the saccharide hydroxyl group; E is methylene or a carbonyl; and A is
wherein R 2 and R 3 are the same or different and are each alkyl comprising 1 to 4 carbon atoms or aryl optionally substituted, or R 2 and R 3 are combined with each other to form an alkylene having 2 or 4 carbon atoms, further wherein the alkylene is optionally substituted with alkyl having 1 to 4 carbon atoms or optionally comprises an intervening phenylene; and m′ and n′ are each an integer of 0 or 1;
and Q 2a is one of the groups given below,
A 1 is
R 2′ and R 3′ are the same or different and are each alkyl comprising 1 to 4 carbon atoms or aryl optionally substituted, or R 2′ and R 3′ are combined with each other to form an alkylene having 2 or 4 carbon atoms, further wherein the alkylene is optionally substituted with alkyl having 1 to 4 carbon atoms or optionally comprises an intervening phenylene; m′ and n′ are each an integer of 0 or 1;
R 7 , R 8 , R 9 are the same or different and are each a protective group for the saccharide hydroxyl group;
E 1 is methylene or carbonyl;
Z 2 is a group —S—R 1′ , a group —SO—R 1′ , a group —Se—R 1′ , a group —O—C(═NH)CX′ 3 , a halogen atom, an alkoxyl, an alkenyloxy, a group —P(OR 1′ ) 3 or a group —PO(OR 1′ ) 3 ; R 1′ is an alkyl comprising 1 to 20 carbon atoms, an aryl optionally substituted, or a heteroaromatic group; and
X′ is a halogen atom.