A catalytic asymmetric conjugate hydrophosphination of α,β-unsaturated amides is accomplished by virtue of the strong nucleophilicity of copper(I)-PPh 2 species, which provides an array of chiral phosphines bearing an amide moiety in high to excellent yields with excellent enantioselectivity. Furthermore, the dynamic kinetic resolution of unsymmetrical diarylphosphines (HPAr 1 Ar 2 ) is successfully carried out through the copper(I)-catalyzed conjugate addition to α,β-unsaturated amides, which affords P-chiral phosphines with good-to-high diastereoselectivity and high enantioselectivity. 1 H NMR studies show that the precoordination of HPPh 2 to copper(I)-bisphosphine complex is critical for the efficient deprotonation by Barton's Base. Moreover, the relative stability of the copper(I)-(R,R P )-TANIAPHOS complex in the presence of excessive HPPh 2 , confirmed by 31 P NMR studies, is pivotal for the high asymmetric induction, as the ligand exchange between bisphosphine and HPPh 2 would significantly reduce the enantioselectivity. At last, a double catalytic asymmetric conjugate hydrophosphination furnishes the corresponding product in high yield with high diastereoselectivity and excellent enantioselectivity, which is transformed to a chiral pincer palladium complex in moderate yield. This chiral palladium complex is demonstrated as an excellent catalyst in the asymmetric conjugate hydrophosphination of chalcone.

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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.