Mechanochemical Nickel-Catalyzed Carbon-Sulfur Bond Formation between Aryl Iodides and Aromatic Sulfur Surrogates.

Abstract

The formation of aromatic thioethers from C-S coupling is of great importance in synthetic chemistry. Traditional solution strategies through transition-metal catalysis generally require bulk solution, heat, and longer reaction time. Herein, a mechano-promoted sulfenylation of aryl iodides with nickel catalysis is described. The active aromatic sulfide agents are in-situ generated from aromatic thiol or disulfide and subsequently adapted in the nickel catalytic cycle, with a tolerance of broad substituted groups under optimized conditions. In addition to the gram-scale synthesis that reveals the application potential of the method, the radical trapping and competitive experiments are also conducted for the mechanistic study, thus providing a plausible mechanism rationally. Furthermore, the proposed methodology is certificated as being versatile and following the green principles with ideal calculated values of green chemistry metrics, and the comparison with other approaches for C-S bond formation is also demonstrated.