Chiral Covalent Organic Frameworks with High Chemical Stability for Heterogeneous Asymmetric Catalysis

Abstract

Covalent organic frameworks (COFs) featuring chirality, stability, and function are of both fundamental and practical interest, but are yet challenging to achieve. Here we reported the metal-directed synthesis of two chiral COFs (CCOFs) by imine-condensations of enantiopure 1,2-diaminocyclohexane with <i>C</i>₃-symmetric trisalicylaldehydes having one or zero 3-<i>tert</i>-butyl group. Powder X-ray diffraction and modeling studies, together with pore size distribution analysis demonstrate that the Zn­(salen)-based CCOFs possess a two-dimensional hexagonal grid network with AA stacking. Dramatic enhancement in the chemical stability toward acidic (1 M HCl) and basic (9 M NaOH) conditions was observed for the COF incorporated with <i>tert</i>-butyl groups on the pore walls compared to the nonalkylated analog. The Zn­(salen) modules in the CCOFs allow for installing multivariate metals into the frameworks by postsynthetic metal exchange. The exchanged CCOFs maintain high crystallinity and porosity and can serve as efficient and recyclable heterogeneous catalysts for asymmetric cyanation of aldehydes, Diels–Alder reaction, alkene epoxidation, epoxide ring-opening, and related sequential reactions with up to 97% ee