Glycosylation via locked anomeric configuration: stereospecific synthesis of oligosaccharides containing the beta-D-mannopyranosyl and beta-L-rhamnopyranosyl linkage.
cis-1,2-Stannylene acetals of D-mannose and L-rhamnose, formed preferentially from the free sugars treated with dibutyltin oxide, are capable of displacing the trifluoromethanesulfonyl (triflyl) leaving groups in carbohydrates to give, with retention of configuration at the anomeric center in the nucleophile, cis-1,2-linked oligosaccharides. In the case of secondary triflates, the new glycosidic linkage is formed with complete inversion of configuration in the electrophile. Both the reactivity of the electrophile and nucleophilicity of oxygens in the stannylene complex affect the overall outcome of the reaction. From the comparison of results of a number of glycosylations via stannylene acetals, it appears that nucleophilicity of oxygens involved in the cis-1,2-acetals decreases in the order: equatorial anomeric > equatorial non-anomeric > axial anomeric. Consequently, treatment of the stannylene acetal prepared from D-mannose (mainly the cis-1,2-stannylene compound in admixture with a small proportion of the cis-2,3-stannylene acetal) with methyl 2,3,4-tri-O-benzoyl-6-O-trifluoromethanesulfonyl-alpha-D-glucopyra noside yielded, in addition to the expected beta-D-mannopyranoside (major), a product of non-anomeric alkylation at O-3. On the other hand, glycosylation of the stannylene acetal derived from maltose with methyl 2,3,6-tri-O-benzoyl-4-trifluoromethanesulfonyl-alpha-D-galactopyra noside gave almost exclusively a non-glycosidically, (2-->4)-linked pseudo-trisaccharide. Combination of the glycosylation via locked anomeric configuration with conventional glycosylations, to yield higher oligosaccharides, is also demonstrated.
Hodosi
G
G
NIDDK, National Institutes of Health, Bethesda, MD 20892-0815, USA.
Kovác
P
P
D002236:Carbohydrate Conformation; D002240:Carbohydrate Sequence; D006031:Glycosylation; D008358:Mannose / Q000737:chemistry*; D008969:Molecular Sequence Data; D009844:Oligosaccharides / Q000138:chemical synthesis* / Q000737:chemistry; D012210:Rhamnose / Q000737:chemistry*; D013237:Stereoisomerism
D009844:Oligosaccharides; D008358:Mannose; D012210:Rhamnose