Divergent Hydroxysulfenylation and Chlorosulfonylation of Styrenes with Sulfinyl Chlorides Steered by Controlled Disproportionation of Sulfoxide‐Onium Ions

Abstract Herein, sulfinyl chlorides and styrenes have been exploited to afford either β‐hydroxy‐phenylethyl sulfides catalyzed by homogenous ZnCl 2 , or β‐chloro‐phenylethyl sulfones mediated by heterogeneous CuO nanoparticles (NPs). The key to achieve such a divergent synthetic strategy is the controlled disproportionation process of sulfoxide‐onium ions, induced by different metal complexes. Owing to the mild conditions, a wide range of functional groups and heterocycles could be tolerated by both of the protocols. The mechanistic studies reveal the key role of sulfoxide‐onium ions in both of the reaction pathways, and suggest that metal‐steered disproportionation defines the oxidation state of sulfur in products.