Electrochemically Induced Synthesis of β‐Ketosulfones from Enol Acetates and Sodium Sulfinates

Abstract β‐Ketosulfones were synthesized from enol acetates and sodium sulfinates under electrochemical conditions. The starting sulfinates can act both as the supporting electrolyte and as the source of S‐centered radicals, allowing electrolysis to proceed without external salt. Side reactions of enol acetates’ oxidation are not observed, and the developed process is quite selective. The proposed electrochemical sulfonylation is compatible with a wide range of the initial enol acetates and sulfinates. On the basis of literature data, control experiments, and CV studies, the presumable reaction pathway is suggested. The key intermediates are S‐centered sulfonyl radical, C‐centered benzylic radical, and β‐acetoxy‐β‐hydroxysulfone.