Directed <i>Ortho</i>-Lithiation of Aminophosphazenes: An Efficient Route to the Stereoselective Synthesis of <i>P</i>‑Chiral Compounds

Ortho-directed lithiation of P,P-diphenylaminophosphazenes followed by electrophilic quench is described as an efficient process for synthesizing P-chiral ortho-functionalized derivatives in high yields and diastereoselectivities. The method allows the tunable preparation of structurally diverse enantiopure P-chiral compounds including phosphinic and phosphinothioic amides, phosphinic esters, phosphine oxides, and o-aminophosphines.