Enantioselective Synthesis of H‐Phosphinamidates

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.