Efficient electrophilic and nucleophilic epoxidations utilizing a sulfonylperoxy radical and peroxysulfate species

Abstract

Reaction of superoxide anion radical (O-2(-.)) with o-nitrobenzenesulfonyl chloride yields a o-nitrobenzenesulfonyl peroxy radical with strong oxidizing ability, which is capable of oxidizing aryl methylene moieties to aryl ketones and relatively electron-rich alkenes regioselectively to epoxides. The oxidizing species is tentatively attributed to the o-nitrobenzenesulfonyl peroxy radical of structure 1. Tetrabutylammonium peroxydisulfate ((TBA)(2)S2O8, 2) was prepared by the reaction of tetrabutylammonium hydrogen sulfate with potassium peroxydisulfate. The epoxidation of enals and enones, such as alpha,beta-unsaturated aldehydes or ketones, was efficiently achieved with 2 in the presence of hydrogen peroxide and base in acetonitrile or in methanol at 25degreesC A base-sensitive substrate, such as cinnamaldehyde, could be successfully epoxidized under mild reaction conditions and in short reaction time. (C) 2002 Wiley Periodicals, Inc.