Generation and reactions of thiirenium ions by the Cation Pool method

Abstract

Thiirenium ions generated and accumulated by low-temperature electrochemical oxidation of disulfides in the presence of alkynes were successfully observed by low-temperature NMR, Raman, and mass spectroscopies and were found to be stable at temperatures below -40 °C. The thiirenium ions showed ambident reactivity toward subsequently added nucleophiles to give either disubstituted alkenes or alkynes depending on the nature of the nucleophiles.