Catalytic C−H Bond Stannylation: A New Regioselective Pathway to C−Sn Bonds via C−H Bond Functionalization

The ubiquitous Stille coupling reaction utilizes Sn−C bonds and is of great utility to organic chemists. Unlike the B−C bonds used in the Miyaura−Suzuki coupling reaction, which are readily obtained via direct borylation of C−H bonds, routes to organotin compounds via direct C−H bond functionalization are lacking. Here we report that the nickel-catalyzed reaction of fluorinated arenes and pyridines with vinyl stannanes does not provide the expected vinyl compounds via C−F activation but rather provides new Sn−C bonds via C−H functionalization with the loss of ethylene. This mechanism provides a new unanticipated methodology for the direct conversion of C−H bonds to carbon−heteroatom bonds.