The asymmetric conjugate addition of medium order alkyl cuprate reagents, R(5)Cu(3)Li(2), to 2-cyclohexen-1-one, 2-cyclopenten-1-one and 2-cyclohepten-1-one, with the help of phosphorus ligand B*, is described. 3-Alkyl substituted cyclohexanones are obtained in essentially optically pure form. The same chiral ligand, associated with CuI, in catalytic amount (10%), allows the asymmetric conjugate addition of Et(2)Zn to 2-cyclohexen-1-one.