A series of optically pure 尾-amino ketones have been synthesized in high enantioselectivities (ee > 99%) by Rh-DuanPhos-catalyzed asymmetric hydrogenation of readily prepared 尾-keto enamides. Further reduction of these 尾-amino ketones with hydrogen and Pd/C leads to the formation of a variety of protected enantiomerically pure 纬-aryl amines (ee > 99%), which are key building blocks in many bioactive molecules.