Photocatalytic EnT-Mediated Aminophosphorylation of Alkenes Using Oxime Esters as Bifunctional Reagents

C–P bond formation has typically been achieved by a single-electron transfer process. Herein, a novel class of oxime ester bifunctionalization reagents were first applied to the photocatalytic β-aminophosphorylation of modular olefins. The bifunctional reagents generate two distinct radical species (imine and phosphoryl radicals) that exhibit excellent regioselectivity. Subsequently, these radicals are attached to the olefins through a single-step EnT catalytic process, establishing a novel synthetic pathway. This protocol is characterized by excellent regioselectivity, broad functional group tolerance, and mild reaction conditions, which would enrich the diversity and versatility to facilitate the diversity-oriented synthesis of β-aminophosphorylated complex molecule scaffolds.