Cathodic cleavage of sulfones: formation of phenolate from strongly activated aryl sulfones

Electrogenerated radical-anions of 1,4-bis(alkylsulfonyl)benzenes can under go two modes of reversible bond cleavage (depending on the stability of the alkyl radical) to afford alkylated monosulfones and phenolates, the latter of which can be trapped as ethers by reaction with electrophiles (alkyl io dides). For starting materials with primary and secondary alkyl moieties, w e propose that the initially formed radical-anions rearrange (via an electr ophilic aryl radical) to give aryl sulfinate radical-anions which decompose to yield phenolates and alkyl radicals. (C) 2000 Elsevier Science S.A. All rights reserved.