Catalytic enantioselective construction of tetrasubstituted carbons by self-assembled poly rare earth metal complexes.

Rare earth metal-based enantioselective catalysts that can promote practical cyanation reactions of ketones and ketoimines were developed. These catalytic enantioselective tetrasubstituted carbon-forming reactions are useful platforms for the synthesis of biologically active compounds. ESI-MS and crystallographic studies of the asymmetric catalysts revealed that the active catalysts are polymetallic complexes produced through the assembly of modules. The higher-order structure of the polymetallic complexes has strong effects on catalyst activity and enantioselectivity. Controlling the higher-order structure of artificial polymetallic asymmetric catalysts is a new strategy for optimizing asymmetric catalysts. Recent progress in this approach is also described.