Recent advances from our group in the design and applications of multimetallic bifunctional asymmetric catalysts are described. Suitable design of chiral ligands and selection of metals were important to realize cooperative bimetallic catalysis. In this account, our strategies for constructing flexible and diverse chiral environments in multimetallic complexes for the rapid optimization of targeted reactions, such as tertiary nitroaldol kinetic resolution, cyclopropanation of electron-deficient olefins, cyano- ethoxycarbonylation of aldehydes, direct Mannich-type reactions, the nitro-Mannich reaction, the anti-selective nitroaldol reaction, and animation, are discussed in detail. 1 Introduction 2 Heterobimetallic Rare-Earth-Alkali Metal-BINOL Complexes 2.1 Background 2.2 Catalytic Kinetic Resolution of Tertiary Nitroaldols 2.3 Catalytic Asymmetric Cyclopropanation of Enones 2.4 Catalytic Asymmetric Cyano-ethoxycarbonylation 3 La Aryloxide/Li Aryloxide/pybox Complexes for Direct Catalytic Asymmetric Mannich-type Reactions 4 Heterobimetallic Transition Metal/Rare-Earth Metal/Dinu-cleating Schiff Base Complexes 4.1 syn-Selective Nitro-Mannich-type Reaction 4.2 anti-Selective Nitroaldol Reaction 5 Homobimetallic Nickel/Dinucleating Schiff Base Complex 6 Rare-Earth Metal/Amide Complexes for Catalytic Asymmetric Amination 7 Summary.
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