Solvolytic Behaviors of O-Benzoyl, Cyclic O, O-Thionocarbonate, and O, S-Thiolcarbonate Groups in 3-O-Benzoyl-1, 2-O-isopropylidene-α-D-glucofuranose Derivatives

Abstract

O-Benzoyl, cyclic thionocarbonate, and thiolcarbonate groups in 5, 6-O-thiono-, 5, 6-O, S-thio-l, and 5, 6-S, O-thiolcarbonates of 3-O-benzoyl-1, 2-O-isopropylidene-α-D-glucofuranoses behaved differently on solvolysis under alkaline conditions. Generally, the 3-O-benzoyl group was the most vulnerable to NaOH in water or MeOH, while thionocarmonate and thiolcarbonate groups were more reactive than the O-benzoyl group toward methanolysis with NaOMe. In particular, methanolysis of the 5, 6-S, O-thiolcarbonate with NaOMe gave a thiirane derivative very rapidly.