Regioselective benzoylation of glycopyranosides by benzoic anhydride in the presence of Cu(CF3COO)2

[Display omitted] ► Regioselective benzoylation of glycosides in the presence of Cu(CF3COO)2 is studied. ► The probable mechanism of regioselective benzoylation of diols is given. ► The simple syntheses of the monobenzoates of some glycopyranosides are offered. Benzoylation of methyl and benzyl glycopyranosides by benzoic anhydride in acetonitrile in the presence of copper(II) trifluoroacetate as a promoter has given monobenzoates with a good yield and high regioselectivity. The composition of monobenzoates depended both on a configuration of hydroxyl groups and on a configuration of aglycone. The simple syntheses of the monobenzoates of some glycosides are offered.