Bimetallic Catalysts Based on Chiral Amplification, Inversion, and Assembly for an Asymmetric Cascade Process

Designing heterogeneous catalysts to mimic complicated biological processes and exploring methods to precisely modulate their chirality is crucial for asymmetric reactions. In this study, two chiral catalysts were immobilized on the non-helical C-C polymers, achieving amplification and reversible reversal of polymer chirality by altering the copolymer structure and solvent. Additionally, the copolymer undergoes a layered assembly process with solvent changes, resulting in reversible regulation of its superhelical fiber structure (P or M configuration). At high concentrations, it aggregates to form a knitting wool ball-like hyperhelical three-dimensional structure. A strong correlation has been established between the chirality and catalytic selectivity of the catalyst in the decarboxylative Mannich reaction/asymmetric transfer hydrogenation enantioselective cascade reaction. This bimetallic catalyst produces two chiral products in catalytic asymmetric cascade reactions with high catalytic activity and excellent enantioselectivity, achieving the "one stone, two birds" effect. It can be reused 10 times without significant losss of catalytic activity or stereoselectivity. This copolymerization synthesis strategy may contribute to the development of new polymer catalyst with controllable chirality and superhelical structure.