The dinuclear L1-Pd2 complex binds to malononitrile at both nitrogen atoms of the nitrile moieties. Although the formation of palladium enolate by simple mixing of malononitrile with L1-Pd2 is suggested by the detection of an ion peak for [L1(−2H) + Pd2 + NCCHCN]+ at m/z = 1123.1764, the addition of Zn(OAc)2 also assists the smooth formation of the palladium enolate. The low asymmetric induction and catalyst activity of the mono-nuclear palladium complex using L6 and L7 suggest the effective role of the dinuclear palladium complex for converting 2a to 3a (Table 1, entries 13, 14) Moreover, because asymmetric induction of the Mannich adducts 2a and 3a is strongly influenced by the selection of hard metal salts, as shown in Table 1, a Zn(OAc)2-driven reactant is incorporated in the asymmetric reaction sphere45–53. When the hard zinc atom is captured by the two hard phenoxy oxygens of L1-Pd2, the zinc atom can act as a Lewis acidic site for activating Boc-imines. During nucleophilic attack by the Pd-enolate malononitrile of the zinc-activated N-Boc imine, the approach shown in model A (Fig. 6) involves serious steric repulsion between a benzene ring from the phosphine in L1 and the N-Boc imine. By flipping the face of the N-Boc imine, as shown in Model B, the steric repulsion can be released, and nucleophilic attack of the Re-face of the N-Boc imine gives the (R)-enriched Mannich product.