Topology-Encoded Asymmetric Tandem Catalysis in BINAP-Based Metal-Organic Frameworks.

Achieving efficient asymmetric tandem catalysis in heterogeneous systems remains a fundamental challenge, as it requires the simultaneous integration of chiral confinement, structurally defined active sites, and compatibility across multiple reaction steps within robust solids. Here, we demonstrate that framework topology can encode ligand conformation and catalytic function in the solid state. An enantiopure tetratopic BINAP-derived linker (BINAP = 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl) is assembled into chiral metal-organic frameworks with distinct network topologies, which impose topology-dependent torsional expansion or contraction of the BINAP backbone and thereby generate well-defined modes of chiral confinement. Postsynthetic incorporation of Pd and Rh centers affords heterogeneous catalysts with atomically resolved coordination environments, enabling direct correlations between framework topology, ligand conformation, and catalytic reactivity. These catalysts promote asymmetric tandem coupling/[2 + 2] cycloaddition and 1,4-addition/hydrogenation reactions with high efficiency, delivering enantioselectivities of up to 99% ee and diastereomeric ratios of up to 11.5:1, while maintaining excellent stability and recyclability. These results establish topology-encoded control as an efficient strategy for enabling predictable asymmetric tandem catalysis in heterogeneous framework catalysts.