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

Abstract

AbstractHerein, 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 31P 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 H2O2 is transformed to a chiral diarylphosphinate in high yield with retained enantioselectivity, which allows further transformations towards various P‐chiral tertiary phosphines.