Direct Synthesis of Chiral Tertiary Diphosphines via Pd(II)-Catalyzed Asymmetric Hydrophosphination of Dienones

A highly diastereo- and enantioselective Pd(II)-catalyzed hydrophosphination of dienones with Ph2PH involving formation of double C*-P bonds has been developed, providing a series of chiral tertiary diphosphines (chiral PCP pincer ligands) in high yields. A catalytic cycle for the reaction was proposed.