Elsevier

Tetrahedron

Volume 54, Issue 29, 16 July 1998, Pages 8321-8348
Tetrahedron

Direct chemical synthesis of β-mannopyranosides and other glycosides via glycosyl triflates

https://doi.org/10.1016/S0040-4020(98)00426-8Get rights and content

Abstract

High yield, highly stereoselective methods for the synthesis of β-mannopyranosides of primary, secondary, and tertiary alcohols are presented. Activation of mannosyl sulfoxides or mannosyl thioglycosides with trifluoromethanesulfonic anhydride or benzenesulfenyl triflate, respectively, leads to the efficient formation of α-mannosyl triflates at −78 °C in dichloromethane, in the presence of 2,6-di-tert-butyl-4-methylpyridine. These triflates then react SN2-like with alcohols to give the β-mannosides. The use of a 4,6-O-benzylidene protected mannose is required for high selectivity, as is the use of non-participating protecting groups on O-2 and O-3 of the donors. It is further demonstrated that the thioglycoside/benzenesulfenyl triflate activation is applicable in the glucoside series, when both armed and disarmed protecting groups are tolerated.

Two new methods for the formation of α-mannosyl triflates and, by SN2-like displacement, β-mannosides in excellent yield and selectivity are described

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