Although the Mannich reaction was smoothly catalyzed by the simple use of L1-Pd2, the Mannich product 2a was obtained with only 8% ee. As we expected cooperative effects due to the phenoxy unit of L1-Pd2 (Fig. 2B), the addition of several hard metal salts was examined (Entries 2–8). Several metal acetates were effective in improving asymmetric induction. With assistance from Zn(OAc)2 or Mg(OAc)2, L1-Pd2 smoothly catalyzed the Mannich reaction to give 2a with 68% ee and 74% ee, respectively. The structure-activity relationship of the ligands is also shown in Table 1. The equivalent catalyst using the methyl analog of L1 ((L2)-Pd2) gave 2a with only 11% ee (entry 9). Although the t-Butyl analog L4-Pd2 gave 2a with 77% ee, the catalyst activity was reduced (entry 11). The diastereomeric ligand L5 synthesized from (S)-BINOL, and L6 and L7 for constructing mono-nuclear palladium complex resulted in low levels of asymmetric induction. For L1-Pd2 with a Zn(OAc)2 catalyst system, when the N-Boc imine 1a was added slowly, the Mannich adduct 2a was obtained with 91% ee in 5 mol % catalyst use (entry 15).