A copper-catalyzed asymmetric addition of diorganozinc reagents to N-phosphinoylimines has been developed for the synthesis of chiral alpha, alpha, alpha-trifluoromethylamines. The trifluoromethyl ketimines, generated in situ from the corresponding hemiaminals, led to the chiral amides in high yields (71-89%) and excellent enantiocontrol (91-99% ee).