Substrate-Controlled Divergent Oxidative Cross-Coupling Reaction via Dual-Chelation-Assisted Strategy: −SMe/–SeMe as Traceless Directing Groups

A dual-chelation-assisted oxidative C8–H/C2–H cross-coupling between 1-chalcogen-substituted naphthalenes and benzamides under the Rh/Ag/HFIP catalytic system is disclosed herein, which features excellent regio- and chemoselectivity. When thiomethyl (−SMe) serves as the directing group, only 2-methoxy-substituted thioethers undergo in situ removal of this directing group, whereas other substrates are resistant to C–S bond cleavage. Replacing thiomethyl with selenomethyl (−SeMe) results in smooth C–Se bond cleavage for all selenoether substrates. This strategy enables a substrate-controlled divergent synthesis of biaryls, and represents the first example of utilizing −SMe and −SeMe as traceless directing groups.