Co-solvent-tunable electroreduction of sulfonyl chlorides to thiosulfonates and disulfides.

A co-solvent-controlled facile and tunable electrochemical protocol has been developed for divergent access to thiosulfonates and disulfides from readily available arylsulfonyl chlorides. By simply switching the alkylaromatic co-solvent (ethylbenzene or toluene), selective formation of two high-value organosulfur compounds was achieved in an undivided cell. This approach avoids the use of metal catalysts, external redox reagents, and sacrificial anodes, demonstrating a sustainable and practical strategy. A wide range of arylsulfonyl chlorides underwent the transformation smoothly with good functional group tolerance and satisfactory yields. Mechanistic investigations including cyclic voltammetry, radical trapping experiments, and product analysis revealed a radical-involved pathway, where anodic oxidation of alkylaromatics precisely modulates the cathodic reduction pathway to realize switchable synthesis.