Activation of Superoxide : Application of Peroxysulfur Intermediates to Organic Synthesis

Abstract

For the activation of superoxide anion radical (O2-.), O2-. was reacted with arenesufonyl or arenesulfinyl-chlorides at -20 - 30-degrees-C to generate the corresponding new arenesulfonylperoxy- or arenesulfinylperoxy radical intermediates. These peroxysulfur intermediates show excellent oxidizing abilities for the regioselective epoxidations of olefins, oxidative desulfurizations of thiocarbonyls to carbonyls, cleavages of C=N to C=O and conversion of the benzylic methylene groups to ketones under mild conditions at ca. -20-degrees-C. The formation of these peroxy intermediates have been also confirmed by the spin trapping studies by ESR.