Tandem Arbuzov-Perkow reaction: general synthesis of α-substituted vinyl P(V)-compounds

α-Substituted vinyl P(V)-molecules are important scaffolds with wide applications. Although several synthetic methods have been developed, few of them are equally feasible for the general synthesis of different types of P(V)-structures. Herein, we developed a benign tandem Arbuzov-Perkow reaction between the readily available chloroacetyl chloride and various P(III)-reagents, delivering the corresponding enol bisphosphorus compounds in high yields. The subsequent Negishi coupling reaction via selective cleavage of the P(O)O-C(sp²) bond enabled efficient introduction of a (hetero)aryl or a (cyclo)alkyl group onto the P-adjacent C(sp²)-carbon, affording diverse α-substituted terminal alkenyl phosphonates, phosphinates, and phosphine oxides with generally good to excellent yields, respectively.