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.