Highly stereoselective synthesis of primary, secondary, and tertiary α-S-sialosides under Lewis acidic conditions.

N-acetyl 4-O,5-N-oxazolidinone protected sialyl phosphates of either anomeric configuration are excellent donors for the formation of α-S-sialosides at -78 °C in dichloromethane with primary, secondary, and tertiary thiols including galactose 3-, 4-, and 6-thiols. The reactions, which proceed under typical Lewis acid promoted glycosylation conditions, are highly α-selective and do not suffer from competing elimination of the phosphate.