Novel, chiral Lewisbase organocatalysts, which displayed poor enantioselection in the hydrosilylation of N-aryl β-enamino esters, were found to be the catalysts of choice in the hydrosilylation of α-imino esters. In the presence of 10 mol-% of the best catalyst, various α-imino esters underwent enantioselectivehydrosilylation to provide a wide range of chiral α-amino esters with good yields (up to