A novel approach to the synthesis of a variety of aminodeoxy-α-D-glycopyranosides

Conditions for the replacement of the 3-acetoxy group of ethyl 3,4,6-tri-O-acetyl-2-deoxy-2-oximino-α-D-arabino-hexopyranoside (1) by nucleophiles including azide, phthalimide, hydride, and thiophenoxide are reported. The reaction was discovered through the formation of dimeric and trimeric derivatives of deacetylated 1 in the course of its alkaline hydrolysis. The possible use of the replacement reaction to achieve precursors for the formation of 3-deoxy-, 3-amino-3-deoxy-, 2-amino-2,3-dideoxy-, 2,3-diamino-2,3-dideoxy-, and 2-amino-2,3,4-trideoxy-α-glycopyranosides is demonstrated.