For N-Boc-imines derived from both electron-donating and electron-deficient benzaldehydes, chiral 1,3-diamines were obtained in a highly enantioselective manner. A chiral bisfuryl-1,3-diamine(3i) was obtained with 86% ee, and a bisnaphthyl-1,3-diamine(3j) was also obtained successfully with 91% ee. When the second Mannich reaction was examined using rac-2a with N-Boc-imine, 3a was obtained in 73% ee with increasing co-production of the meso-form in dl/meso = 1:1. This result suggests that the second Mannich reaction is catalyzed independently from the first Mannich reaction, and the enantiomeric excess of 3a is improved due to the meso-trick44.