Diastereoselective Synthesis of Phosphinyl Peptides via Rh-Catalyzed 1,4-Addition in Coparticipation of a P -Chiral Moiety and Difluorphos.

The asymmetric Rh-catalyzed 1,4-addition of aryl/heteroaryl moieties to α,β-unsaturated esters was achieved in high diastereoselectivity via the coparticipation of a P -chiral phosphinyl moiety at Cβ to the prochiral center and ( R )- or ( S )-Difluorphos. This methodology expands the synthetic toolbox available for the preparation of structurally diverse chiral phosphinyl peptides.