Document Detail


A synthetic approach to polysialogangliosides containing alpha-sialyl-(2-->8)-sialic acid: total synthesis of ganglioside GD3.
MedLine Citation:
PMID:  8370046     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
A stereocontrolled, facile total synthesis of ganglioside GD3 is described as an example of a proposed systematic approach to the preparation of gangliosides containing an alpha-sialyl-(2-->8)-sialic acid unit alpha-glycosidically linked to O-3 of a D-galactose residue in their oligosaccharide chains. Glycosylation of 2-(trimethylsilyl)ethyl 6-O-benzoyl-, 3-O-benzoyl-, or 3-O-benzyl-beta-D-galactopyrano-sides, or 2-(trimethylsilyl)ethyl 2,3,6,2',6'-penta-O-benzyl-beta-lactoside (7), with methyl [phenyl 5- acetamido-8-O-(5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D- glycero-alpha-D-galacto-2-nonulopyranosylono-1',9 lactone)- 4,7-di-O-acetyl-3,5-dideoxy-2-thio-D-glycero-D-galacto-2-nonulopyrano sid] onate (3), using N-iodosuccinimide-trifluoromethanesulfonic acid as a promoter, gave the corresponding alpha glycosides 8 (32%), 13 (33%), 14 (48%), and 17 (31%), respectively. The glycosyl donor 3 was prepared from O-(5-acetamido-3,5-dideoxy-D-glycero-alpha-D-galacto-2-nonulopyranosy lonic acid)-(2-->8)-5-acetamido-3,5- dideoxy-D-glycero-D-galacto-2-nonulopyranosonic acid by treatment with Amberlite IR-120 (H+) in methanol, O-acetylation, and subsequent replacement of the anomeric acetoxy group with phenylthio. Compound 8 was converted into the methyl beta-thioglycoside via O-benzoylation, replacement of the 2-(trimethylsilyl)ethyl group by acetyl, and introduction of the methylthio group by reaction with methylthiotrimethylsilane. Compound 17 was converted, via O-acetylation, selective removal of the 2-(trimethylsilyl)ethyl group, and reaction with trichloroacetonitrile, into the alpha-trichloroacetimidate, which was coupled with (2S,3R,4E)-2-azido-3-O-benzoyl-4-octadecene-1,3-diol to give the beta-glycoside. This glycoside was easily transformed, via selective reduction of the azido group, condensation with octadecanoic acid, O-deacylation, and hydrolysis of the methyl ester and lactone functions, into ganglioside GD3.
Authors:
H Ishida; Y Ohta; Y Tsukada; M Kiso; A Hasegawa
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Publication Detail:
Type:  Journal Article; Research Support, Non-U.S. Gov't    
Journal Detail:
Title:  Carbohydrate research     Volume:  246     ISSN:  0008-6215     ISO Abbreviation:  Carbohydr. Res.     Publication Date:  1993 Aug 
Date Detail:
Created Date:  1993-10-13     Completed Date:  1993-10-13     Revised Date:  2006-11-15    
Medline Journal Info:
Nlm Unique ID:  0043535     Medline TA:  Carbohydr Res     Country:  NETHERLANDS    
Other Details:
Languages:  eng     Pagination:  75-88     Citation Subset:  IM    
Affiliation:
Department of Applied Bioorganic Chemistry, Gifu University, Japan.
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MeSH Terms
Descriptor/Qualifier:
Carbohydrate Sequence
Disaccharides / chemistry*
Gangliosides / chemical synthesis*
Glycosides / chemistry
Glycosylation
Molecular Sequence Data
N-Acetylneuraminic Acid
Sialic Acids / chemistry*
Stereoisomerism
Thioglycosides / chemistry
Chemical
Reg. No./Substance:
0/Disaccharides; 0/Gangliosides; 0/Glycosides; 0/Sialic Acids; 0/Thioglycosides; 131-48-6/N-Acetylneuraminic Acid; 62010-37-1/ganglioside, GD3

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