Collaborative\nReduction-Induced Nickel-Catalytic Selective\nC–S Coupling of Aryl Di/Trithiosulfonates with Aryl Halides

Metal-catalytic conversion of polysulfide reagents is\na major challenge\nin organic synthesis due to its challenging activation modes of multiple\nS–S bonds. The utilization of aryl di- and trithiosulfonates\nin nickel-catalyzed reductive coupling with aryl halides has been\nunexplored. Herein, we unprecedentedly describe PPh<sub>3</sub> and\nZn-collaborative reduction-induced nickel-catalytic selective C–S\ncoupling of aryl di/trithiosulfonates with aryl halides to access\nsulfides over common disulfides or trisulfides. Diverse mechanistic\nstudies indicate that the key design of such a reaction could be attributed\nto the employment of PPh<sub>3</sub> and MgCl<sub>2</sub>, which collaborate\nwith Zn for the improved reduction potential that enables selective\nreductive cleavage of PhSO<sub>2</sub>(S)<sub><i>n</i></sub>aryl (<i>n</i> = 2, 3) to electrophilic sulfur species\nfor reductive sulfuration in a controllable fashion.