Diastereoselective\nSynthesis of Phosphinyl Peptides\nvia Rh-Catalyzed 1,4-Addition in Coparticipation of a <i>P</i>‑Chiral Moiety and Difluorphos

The asymmetric Rh-catalyzed 1,4-addition of aryl/heteroaryl\nmoieties\nto α,β-unsaturated esters was achieved in high diastereoselectivity\nvia the coparticipation of a <i>P</i>-chiral phosphinyl\nmoiety at Cβ to the prochiral center and (<i>R</i>)- or (<i>S</i>)-Difluorphos. This methodology expands\nthe synthetic toolbox available for the preparation of structurally\ndiverse chiral phosphinyl peptides.