N−H ketoimines 3a−3v are readily prepared in high yield via organometallic addition to nitriles and isolated as corresponding bench-stable hydrochloride salts. Homogeneous asymmetric hydrogenation of unprotected N−H ketoimines 3a−3v using Ir-(S,S)-f-binaphane as catalyst provides chiral amines 4a−4v in 90−95% yield with enantioselectivities up to 95% ee.