Solvolytic behaviors of O-benzoyl, cyclic O,O-thionocarbonate, and O,S-thiolcarbonate groups in 3-O-benzoyl-1,2-O-isopropylidene-alpha-D-glucofuranose derivatives

O-Benzoyl, cyclic thionocarbonate, and thiolcarbonate groups in 5,6-O-thiono-, 5,6-O,S-thiol-, and 5,6-S,O-thiolcarbonates of 3-O-benzoyl-1,2-O-isopropylidene-alpha-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 thionocarbonate 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.