Au]/[Ag]-Catalyzed Glycosidation of Ethynylcyclohexyl Glycosyl Carbonates Enables Direct Stereoselective Synthesis of 2-Azido-2-deoxy-β-mannopyranosides

Abstract

We describe the [Au]/[Ag]-catalyzed activation of ethynylcyclohexyl 2-azido-4,6-O-benzylidene mannosyl carbonates for β-mannosamine linkage preparation in high yield and selectivity in a temperature- and concentration-dependent manner. VT-NMR studies reveal an anomeric triflate intermediate generated in the absence of an acceptor alcohol that is stable up to −10 °C. The generality of the protocol was illustrated by successful application to a series of acceptors and by synthesis of a fully protected Streptococcus pneumoniae type 19F capsular trisaccharide.