Collaborative Reduction-Induced Nickel-Catalytic Selective C–S Coupling of Aryl Di/Trithiosulfonates with Aryl Halides

Metal-catalytic conversion of polysulfide reagents is a major challenge in organic synthesis due to its challenging activation modes of multiple S-S bonds. The utilization of aryl di- and trithiosulfonates in nickel-catalyzed reductive coupling with aryl halides has been unexplored. Herein, we unprecedentedly describe PPh₃ and Zn-collaborative reduction-induced nickel-catalytic selective C-S coupling of aryl di/trithiosulfonates with aryl halides to access sulfides over common disulfides or trisulfides. Diverse mechanistic studies indicate that the key design of such a reaction could be attributed to the employment of PPh₃ and MgCl₂, which collaborate with Zn for the improved reduction potential that enables selective reductive cleavage of PhSO₂(S)_<i>n</i>aryl (<i>n</i> = 2, 3) to electrophilic sulfur species for reductive sulfuration in a controllable fashion.