Chiral amines, particularly chiral benzylic amines are found in many natural products and pharmaceuticals (Scheme 1A). The established methods for the asymmetric synthesis of chiral amines include reductive amination, 2 olefin hydroamination, 3 and transition-metal-catalyzed coupling of nitrogen nucleophiles with alkyl halides. However, with the aim of streamlining synthesis, the enantioselective amination of benzylic C(sp 3 )-H bonds is highly appealing. Remarkable progress has been made in the catalytic enantioselective nitrene insertion into benzylic C(sp 3 )-H bonds by designing new chiral catalysts (Scheme 1B). Enzyme catalysis has also been demonstrated to be effective for intermolecular asymmetric nitrene C-H insertions. Despite the success of these methods, the limited substrate scope or low level of enantiocontrol preclude their synthetic applications. Therefore, more general and efficient catalytic methods are desired for highly enantioselective intermolecular benzylic C(sp 3 )-H amination.