Highly Stereoselective Synthesis of 2,2-Disubstituted Vinylphosphonates via Aryl to Vinyl 1,4-Palladium Migration

Comprehensive Summary Vinylphosphates play an important role in the fields of synthetic chemistry, pharmaceuticals and material science. It is a long-standing challenge to control the geometry of multi-substituted vinylphosphates. Herein, an efficient method for the synthesis of 2,2-disubstituted vinylphosphonates has been reported. The reaction proceeded via aryl to vinyl 1,4-palladium migration progress, in which two difficulties that the deactivation of palladium catalyst by the coordination of excess secondary phosphine oxide and the competitive cross-coupling to form arylphosphonates are successfully overcome. The judicious selection of phosphine ligand is the key to success. This protocol features excellent regio- and stereoselectivitiy, generally excellent reaction yields and broad substrate socpe.