P-Chiral Phosphines Enabled by Palladium/Xiao-Phos-Catalyzed Asymmetric P–C Cross-Coupling of Secondary Phosphine Oxides and Aryl Bromides

The development of transition metal-catalyzed methods for the synthesis of P-chiral phosphine derivatives pose con-siderable challenge. Herein we present a direct Pd/Xiao-Phos-catalyzed cross-coupling reaction of easily accessible sec-ondary phosphine oxides and aryl bromides, which provides a rapid access to P-chiral phosphine oxides. The reaction proceeds efficiently with a wide array of reaction partners to deliver various tertiary phosphine oxides in up to 96% yield and 97% ee. Moreover, the synthesis of DiPAMP ligand and its analogues was also realized, which demonstrates a suitable pathway to switching the branched chain of DiPAMP.