Catalytic Enantioselective Synthesis of Phosphonamidates from Racemic Phosphonamidites Using Anionic Stereogenic-at-Cobalt(III) Complexes

Catalytic asymmetric oxidation of racemic P(III) species remains largely unexplored and represents a significant challenge compared with the well-established S- or N-oxidation reactions. Herein, we exhibit an efficient bromophosphonium ion-promoted enantioselective synthesis of phosphonamidates from racemic phosphonamidites. By using anionic stereogenic-at-cobalt(III) complexes as catalysts, a variety of chiral phosphonamidates were obtained in high yields with good enantioselectivities (up to 97:3 enantiomeric ratio (er)). Antifungal testing shows these P(V) compounds exhibit broad-spectrum activity, suggesting their potential as fungicides.