Selective C(sp²)–P Cross-Coupling of Alkenylsulfonium Salts with P(O)H Compounds: Divergent Synthesis of Alkenylphosphorus Compounds

Herein, we report a both regioselective and stereoselective method for the formation of C(sp²)-P bonds using alkenylsulfonium salts and >P(O)-H compounds. By employing a palladium catalyst or K₂CO₃, a variety of (<i>E</i>)-alkenylphosphorus compounds and terminal alkenylphosphorus compounds were successfully synthesized with high selectivity. Notably, trisubstituted (<i>Z</i>)-alkenylphosphorus compounds were synthesized for the first time under metal-free conditions. This protocol has a wide substrate scope and good functional group compatibility, providing a direct and highly selective approach for the preparation of various alkenylphosphorus compounds.