The development of framework materials chemistry has provided a powerful platform for constructing porous crystalline systems with precisely controllable structures and integrated functions. Chiral metal-organic frameworks (CMOFs) have attracted considerable interest owing to their ability to immobilize and amplify molecular chirality within crystalline frameworks, offering unique opportunities for asymmetric catalysis. However, the rational organization of multiple catalytic sites within rigid chiral frameworks, as well as the direct involvement of framework structures in stabilizing reaction intermediates and regulating selectivity, remains a significant challenge. Herein, using natural D-camphoric acid as a chiral source, a novel bifunctional ligand was rationally designed and synthesized, enabling the construction of a chiral copper-based metal-organic framework (D-Cam-Cu) featuring a staircase-like three-dimensional architecture. Single-crystal X-ray diffraction analysis reveals that the framework is assembled from paddle-wheel-type dinuclear copper units connected in a layer-by-layer manner, with adjacent layers exhibiting an ordered spatial offset, thereby generating a non-uniform chiral microenvironment. On this basis, the CMOF was integrated with a chiral phosphoric acid to establish a heterogeneous cooperative catalytic system, which was successfully applied to the asymmetric N—H insertion reaction between β-naphthylamine and α-diazocarbonyl esters. Compared with single-catalyst systems, the cooperative system exhibits markedly enhanced reaction yields and enantioselectivities. Combined structural analysis and catalytic investigations suggest that the staircase-like chiral framework plays a crucial role in stabilizing key reaction intermediates, promoting cooperation among multiple active sites, and regulating reaction selectivity. This work not only demonstrates the controllable transformation of natural chiral molecules into functional chiral framework materials but also provides new design principles for developing multifunctional cooperative asymmetric catalytic systems based on framework materials.

Key words: chiral metal-organic frameworks (CMOFs), natural camphoric acid, staircase-like structure, cooperative asymmetric catalysis, N—H bond insertion reaction