Crystallizing Chiral Molecular Catalysts for Heterogeneous Asymmetric Catalysis

The development of chiral heterogeneous catalysts that combine high activity, stability, and stereoselectivity remains a central challenge in asymmetric catalysis. Traditional strategies that immobilize chiral molecular catalysts on amorphous supports typically suffer from non‐uniform active site distribution, poorly defined local environments, and catalyst leaching, which collectively compromise stereocontrol and long‐term stability. Crystallizing chiral molecular catalysts within metal–organic frameworks (MOFs) offers a transformative solution. The inherent crystallinity of MOFs ensures deterministic positioning and uniform distribution of catalytic sites, effectively propagating chirality throughout the framework. Site isolation stabilizes active species and prevents side reactions, whereas confined chiral pockets orient substrates for precise transition‐state control. Moreover, the modular design of MOFs allows fine‐tuning of pore structure and functionality, enabling selective diffusion, cooperative catalysis, and tandem reactions. This perspective outlines strategies for crystallizing chiral molecular catalysts in MOFs and highlights the structural and functional advantages of chiral MOFs (CMOFs) over homogeneous and conventional heterogeneous systems, aiming to inspire innovative CMOF‐based catalysts for sustainable synthesis of high‐value chemicals and pharmaceuticals. We hope this perspective will deepen readers' understanding of CMOF chemistry and inspire the development of innovative CMOF‐based heterogeneous catalysts for the sustainable synthesis of high‐value chemicals and pharmaceuticals.