Copper(I)‐Catalyzed Asymmetric Synthesis of P‐Chiral Aminophosphinites

Abstract Herein, a copper(I)‐catalyzed reaction of diarylphosphines and O ‐benzoyl hydroxylamines is developed. In the cases of symmetrical diarylphosphines, a series of aminophosphinites is prepared in high yields. In the cases of unsymmetrical diarylphosphines, an array of P ‐chiral aminophosphinites is synthesized in high yields with high enantioselectivity by using a copper(I)‐( R , R P )‐Ph‐FOXAP complex as a chiral catalyst. Based on several control experiments and 31 P NMR studies, a two‐electron redox mechanism involving the dynamic kinetic asymmetric transformation of unsymmetrical diarylphosphines is proposed for the copper(I)‐catalyzed asymmetric reaction. Finally, one representative P ‐chiral phosphoric amide generated through the oxidation with H 2 O 2 is transformed to a chiral diarylphosphinate in high yield with retained enantioselectivity, which allows further transformations towards various P ‐chiral tertiary phosphines.