title: Privileged phosphine-based metal-organic frameworks for broad-scope asymmetric catalysis.
abstract: 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.
authors.affiliation: Department of Chemistry, University of Chicago , 929 East 57th Street, Chicago, Illinois 60637, United States.
authors.forename: Joseph M
authors.initials: JM
authors.lastname: Falkowski
authors.forename: Takahiro
authors.initials: T
authors.lastname: Sawano
authors.forename: Teng
authors.initials: T
authors.lastname: Zhang
authors.forename: Galen
authors.initials: G
authors.lastname: Tsun
authors.forename: Yuan
authors.initials: Y
authors.lastname: Chen
authors.forename: Jenny V
authors.initials: JV
authors.lastname: Lockard
authors.forename: Wenbin
authors.initials: W
authors.lastname: Lin