Chiral ferrocene phosphane–carbenes are good ligands for the copper-catalyzed 1, 4- addition of Grignard reagents to various Michael acceptors. The products were obtained in high enantiomeric purity (up to er= 95: 5) and excellent regioselectivity (rr= 99: 1). These ligands are also useful for domino conjugate addition followed by enolate trapping with imine and aldehyde.