Back to results
US 6,632,940 B1Granted
Method for laminaribiose synthesis
AssigneeLaboratoires Goemar S.A.
InventorsJean-Claude Yvin, Frank Jamois, Vincent Ferrieres, Daniel Plusquellec
Life of this patent
Estimating the term…
Abstract
The invention concerns a method for preparing Laminaribiose comprising a step for glycoside binding between a donor and an acceptor of glycosyl. The invention is characterized in that the glycosyl donor is in pyranose form and corresponds to formula (II); the glycosyl acceptor is in furanose form and corresponds to formula (III); said binding step is performed in solution in an anhydrous organic solvent, at a temperature ranging between −80° C. and 40° C., for a time interval ranging between 1 minute and 8 hours, in the presence of a suitable promoter.
Claims14
A method of preparing laminaribiose comprising a step of glycosidic coupling between a glycosyl donor and a glycosyl acceptor, wherein:
- the glycosyl donor is in pyranose form and is of formula (II):
- in which:
- R1 represents:
- an alkyl or haloalkyl radical having 1 to 6 carbon atoms;
- an aryl radical which is non-substituted or substituted with one or more groups selected from the group consisting of a halogen atom, an alkoxy radical having 1 to 6 carbon atoms and a nitro group;
- X represents an electrophilic leaving group selected from the group consisting of:
- a group of formula S(O)nR′ in which R′ represents a radical selected from the group consisting of an alkyl radical having 1 to 6 carbon atoms, an aryl radical which is non-substituted or substituted with an alkoxy group having 1 to 6 carbon atoms, a nitro and acetamide group, and n is an integer equal to 0 or 1 and;
- a trichloroacetimidate group;
- the glycosyl acceptor is in furanose form and is of formula (III)
- in which:
- R2 and R3 together form a radical selected from the group consisting of a methylidyl, ethylidyl, trichloroethylidyl, isopropylidyl, hexafluoroisopropylidyl, cyclopentylidyl, cyclohexylidyl, cycloheptylidyl, butylidyl, 1-tert-butylethylidyl, 1-phenylethylidyl, benzylidyl, methoxybenzylidyl, and 1-phenylbenzylidyl radical;
- and
- R4 and R5 together form a radical selected from the group consisting of a methylidyl, ethylidyl, trichloroethylidyl, isopropylidyl, hexafluoroisopropylidyl, cyclopentylidyl, cyclohexylidyl, cycloheptylidyl, butylidyl, 1-tert-butylethylidyl, 1-phenylethylidyl, benzylidyl, methoxybenzylidyl, or 1-phenylbenzylidyl radical;
- or independently represent a benzyl, acetyl, benzoyl chlorobenzoyl, methoxybenzoyl, nitrobenzoyl, allyl, chlorobenzyl, methoxybenzyl and nitrobenzyl radical;
- said coupling step is carried out in solution in an anhydrous organic solvent, at a temperature between −80° C. and 40° C., for a period of 1 minute to 8 hours, in the presence of a suitable promoter selected from the group consisting of:
- N-bromosuccinimide or N-iodosuccinimide, combined with a Lewis acid selected from the group consisting of ferric chloride, copper ditriflate, tin ditriflate, boron trifluoride dietherate, tin or zirconium tetrachloride, methyl triflate, trimethyl- (or triethyl-) silyl triflate, silver triflate, cadmium ditriflate, cobalt ditriflate, nickel ditriflate, zinc ditriflate, bismuth tritriflate, iron tritriflate, and gallium tritriflate, in the case in which X represents an S(O)nR′ group as defined above in which n is equal to 0,
- a Lewis acid selected from the group consisitng of triflic anhydride, ferric chloride, copper ditriflate, tin ditriflate, boron trifluoride dietherate, tin or zirconium tetrachloride, methyl triflate, trimethyl- (or triethyl-) silyl triflate, silver triflate, cadmium ditriflate, cobalt ditriflate, nickel ditriflate, zinc ditriflate, bismuth tritriflate, iron tritriflate, and gallium tritriflate, combined with an amine, in the case in which X represents an S(O)nR′ group as defined above in which n is equal to 1, and
- a Bronsted acid or a Lewis acid selected from the group consisting of triflic anhydride, ferric chloride, copper ditriflate, tin ditriflate, boron trifluoride dietherate, tin or zirconium tetrachloride, methyl triflate, trimethyl- (or triethyl-) silyl triflate, silver triflate, cadmium ditriflate, cobalt ditriflate, nickel ditriflate, zinc ditriflate, bismuth tritriflate, iron tritriflate, and gallium tritriflate, in the case in which X represents a trichloroacetimidate group;
- and
- the reaction product thus obtained, neutralised and purified, being subjected to a deprotection treatment to give, after purification, laminaribiose.
17 more elements
Laminaribiose synthesis intermediates, which are selected from the following compounds:
- 2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl-(1→3)-1,2:5,6-di-O-cyclohexylidene-α-D-glucofuranose
- and
- 2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl-(1→3)-D-glucopyranose:
A method of preparing laminaribiose comprising a step of glycosidic coupling between a glycosyl donor and a glycosyl acceptor, wherein:
- the glycosyl donor is in pyranose form and is of formula (II):
- in which:
- R1 represents:
- an alkyl or haloalkyl radical having 1 to 6 carbon atoms;
- an aryl radical which is non-substituted or substituted with one or more groups selected from the group consisting of a halogen atom, an alkoxy radical having 1 to 6 carbon atoms and a nitro group;
- X represents a trichloroacetimidate group;
- a the glycosyl acceptor is in furanose form and is of formula (III)
- in which:
- R2 and R3 together form a radical selected from the group consisting of a methylidyl, ethylidyl trichloroethylidyl, isopropylidyl, hexafluoroisopropylidyl, cyclopentylidyl, cyclohexylidyl, cycloheptylidyl, butylidyl, 1-tert-butylethylidyl, 1-phenylethylidyl, benzylidyl, methoxybenzylidyl, and 1-phenylbenzylidyl radical;
- and
- R4 and R5 together form a radical selected from the group consisting of a methylidyl, ethylidyl, trichloroethylidyl, isopropylidyl, hexafluoroisopropylidyl, cyclopentylidyl, cyclohexylidyl, cycloheptylidyl, butylidyl, 1-tert-butylethylidyl, 1-phenylethylidyl, benzylidyl, methoxybenzylidyl, or 1-phenylbenzylidyl radical, or independently represent a benzyl, acetyl, benzoyl, chlorobenzoyl, methoxybenzoyl, nitrobenzoyl, allyl, chlorobenzyl, methoxybenzyl and nitrobenzyl radical;
- said coupling step is carried out in solution in an anhydrous organic solvent, at a temperature between −80° C. and 40° C., for a period of 1 minute to 8 hours, in the presence of a suitable promoter selected from the group consisting of a Bronsted acid or a Lewis acid selected from the group consisting of triflic anhydride, ferric chloride, copper ditriflate, tin ditriflate, boron trifluoride dietherate, tin or zirconium tetrachloride, methyl triflate, trimethyl- (or triethyl-) silyl triflate, silver triflate, cadmium ditriflate, cobalt ditriflate, nickel ditriflate, zinc ditriflate, bismuth tritriflate, iron tritriflate, and gallium tritriflate, in the case in which X represents a trichloroacetimidate group;
- and
- the reaction product thus obtained, neutralised and purified, being subjected to a deprotection treatment to give, after purification, laminaribiose.
11 more elements
Dependencies are inferred from the claim text.