Pd(II)‐Catalyzed Phosphorylation of Enamido C(sp2)–H Bonds: A General Route to β‐Amido‐vinylphosphonates

Abstract Organophosphorus compounds are essential structures in modern pharmaceutical, agrochemical, and material sciences. The development of new and efficient methods for the synthesis of C–P bonds has been an important focus of research. We herein report a Pd‐catalyzed enamido C(sp2)–H phosphorylation for direct construction of C–P bonds under simple and convenient conditions without the need for additional ligands or directing groups. The present reaction can tolerate a wide range of functional groups, and furnish a variety of phosphorylation products including tetrasubstituted‐vinyl β‐aminophosphonates that are otherwise difficult to access. This protocol was also exemplified into the late‐stage modification of bioactive natural products and was suitable for large‐scale synthesis.