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

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,RP )-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 H2 O2 is transformed to a chiral diarylphosphinate in high yield with retained enantioselectivity, which allows further transformations towards various P-chiral tertiary phosphines.