The aldimines and ketimines reacted with alkenes under a rhodium catalyst [Rh(coe)(2)Cl](2) and Cy3P to give mainly the double alkylated products with moderate to high yields. The aldimines bearing H, p-CH3O, p-CH3, p-Cl, p-F, p-CF3 and o-CH3 groups have high reactivities, but m-CH3O, m-Cl and m-F exhibit moderate reactivities. However, o-Cl, o-NO2 and p-NO2 groups did not work. The ketimine 9 gave the mono-alkylated products predominantly. 1-Naphthyl and heteroaromatic aldimines showed good regioselectivities. (C) 2003 Elsevier B.V. All rights reserved.