Interchange Reactions of Aromatic Thiosulfinates

Abstract

Exchange reactions at ambient temperature in the dark between symmetrical aryl Ihiosulfinates Ar-S(0)-S-Ar are described. A polar mechanism involving a four-center transition state is proposed for the reaction. supported by the ea.w of fission of the S-S bond with the polarity introduced by the sulfinyl group. The thiosulfinate exchanges demonstrate a reaction common to a series of thioesters (disulfides/thiosulfnates) and their amides (sulfenamides/sulfinamides) differing in oxidation level of a sulfur atom but under conditions to be correlated with the type of functional group.