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.