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.