Sugar-Pirating as an Enabling Platform for the Synthesis of 4,6-Dideoxyhexoses

An efficient divergent synthetic strategy that leverages the natural product spectinomycin to access uniquely functionalized monosaccharides is described. Stereoselective 2'- and 3'-reduction of key spectinomycin-derived intermediates enabled facile access to all eight possible 2,3-stereoisomers of 4,6-dideoxyhexoses as well as representative 3,4,6-trideoxysugars and 3,4,6-trideoxy-3-aminohexoses. In addition, the method was applied to the synthesis of two functionalized sugars commonly associated with macrolide antibiotics-the 3- O -alkyl-4,6-dideoxysugar d-chalcose and the 3- N -alkyl-3,4,6-trideoxysugar d-desosamine.