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Here, we review the utility of chiral bimetallic (multimetallic) Lewis acidic complexes in catalytic asymmetric transformations. Bimetallic complexes are endowed with dual catalytic functions that synergistically activate multiple substrates and functionalities. This cooperative activation mode is particularly effective for activating low reactivity substrates in a highly stereoselective manner without the aid of stoichiometric activating reagents. The privileged bimetallic catalysts presented here highlight the importance of catalyst design in the development of widely applicable catalytic systems.

A catalytic system comprising functionalized small diamides and rare earth metals (REs) exerts intriguing catalytic properties that are dictated by dynamic construction of flexible molecular spaces. The dynamic interaction of diamides and REs is characterized by broad applicability to distinct reaction systems as well as notable switchable catalysis. Structural modification of the diamide allows for enhanced intermolecular interactions to afford a self-assembled solid-phase catalyst with a specific molecular space that engages in heterogeneous asymmetric catalysis with a continuous-flow platform.