Abstract
P-stereogenic phosphoramidates prove essential in agrochemicals and medicines, but their construction remains a challenge for enantioselective catalysis. We describe a Yttrium-catalyzed desymmetrization supported by Feng-ligands. An achiral oxazolidinyl phosphorodichloridate undergoes enantioselective nucleophilic substitution with phenols at ambient temperatures, followed by a stereospecific addition with amines in one pot. The resulting P-stereogenic phosphoramidate serves as a trifunctional building block to access diverse P-(V) motifs, enabling the stereodivergent synthesis of protected ProTides and the first stereoselective total synthesis of phosmidosine.