Enantioselective Synthesis of H‐Phosphinamidates

Abstract Enantioenriched heteroatom‐containing H‐phosphoryl compounds unite a nucleophilic H–P(O) moiety with an electrophilic, substitutable heteroatom group, endowing them with inherent ambiphilicity and making them powerful platforms for constructing P(V)‐stereogenic molecules—structures of growing significance in asymmetric synthesis, pharmaceuticals, and materials science. Yet their enantioselective synthesis has remained a significant challenge. Here we report the first highly enantioselective synthesis of H‐phosphinamidates. These bifunctional, configurationally stable compounds enable stereospecific H–P(O) transformations to access diverse P–C, P–N, P–O, and P–S linkages, while the amino group offers an orthogonal handle for secondary derivatization. These reactivity features establish H‐phosphinamidates as a versatile and general platform for the modular synthesis of structurally diverse P(V)‐stereogenic compounds.