1,1-Addition of α-C-Bridged Biphospholes with Alkynes

An unusual chemoselective 1,1-addition of α-C-bridged biphospholes to terminal alkynes is reported. The developed protocol provides simple access to the unknown 1,3-diphosphepines, which has potential applications in the coordination and catalyst chemistry. Their Pd and Mo complexes were studied by single-crystal X-ray diffraction analysis. This method features excellent chemoselectivity, high step and atom economy, mild reaction conditions, and wide substrate scope.