We report a promoter-assisted glycosidation approach for the stereoselective synthesis of the 6-deoxy-β-D-mannoheptopyranose oligosaccharides. SphosAuNTf 2 -promoted glycosidation of 6-deoxy-D-manno-heptopyranosyl o-hexynylbenzoate with common alcohols afforded a range of 6-deoxy-D-manno-heptosides with good to excellent β-selectivities. The counterion and the ligand of SPhosAuNTf 2 were found to have a dramatic effect on the formation of the 1,2-cis-β-linked 6-deoxy-D-manno-heptosides. This approach was effectively applied to the stereocontrolled synthesis of the 6-deoxy-β-D-manno-heptopyranose oligosaccharides relevant to Burkholderia pseudomallei and Burkholderia mallei.
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