Privileged Phosphine-Based Metal–Organic Frameworks for Broad-Scope Asymmetric Catalysis

A robust and porous Zr metal–organic framework (MOF) based on a BINAP-derived dicarb­oxyl­ate linker, BINAP-MOF, was synthesized and post-synthetically metalated with Ru and Rh complexes to afford highly enantio­selective catalysts for important organic transformations. The Rh-functionalized MOF is not only highly enantio­selective (up to >99% ee) but also 3 times as active as the homogeneous control. XAFS studies revealed that the Ru-functionalized MOF contains Ru-BINAP pre­catalysts with the same coordination environment as the homogeneous Ru complex. The post-synthetically metalated BINAP-MOFs provide a versatile family of single-site solid catalysts for catalyzing a broad scope of asymmetric organic transformations, including addition of aryl and alkyl groups to α,β-unsaturated ketones and hydrogenation of substituted alkene and carbonyl compounds.