A series of N-formamides derived from pipecolinic acid have been synthesized and tested as Lewis base catalysts for the enantioselective reduction of N-aryl imines by trichlorosilane. Through the investigation of the structure–efficacy relationship between the side amide group and catalytic performance, several highly effective catalysts were discovered. In particular, arylamido-type catalyst 5i and non-arylamido-type catalyst 6c exhibited high reactivity and enantioselectivity, furnishing the reduction of a wide variety of N-aryl imines with high isolated yields (up to 98%) and ee values (up to 96%) under mild conditions. Moreover, these two catalysts complement each other in terms of their tolerances to nonaromatic ketimines and non-methyl ketimines.