Synthesis of Thiosulfonates via CuI‐Catalyzed Reductive Coupling of Arenesulfonyl Chlorides Using Na 2 SO 3 or NaHSO 3 as Reductants

A mild and efficient method for the synthesis of thiosulfonates has been developed through a CuI‐catalyzed reductive coupling of arenesulfonyl chlorides using Na 2 SO 3 or NaHSO 3 as the terminal reductant under a nitrogen atmosphere at room temperature. A broad scope of thiosulfonates was obtained in high to excellent yields via this simple, practical and economical transformation. The ease of handling, the use of low‐cost and readily available reaction materials at room temperature, and the efficiency on a large scale, make this method attractive in both organic synthesis and industrial applications.