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

Autor: Teng Zhang, Takahiro Sawano, Galen Tsun, Jenny V. Lockard, Yuan Chen, Joseph M. Falkowski, Wenbin Lin
Rok vydání: 2014
Předmět:
Zdroj: Journal of the American Chemical Society. 136:5213-5216
ISSN: 1520-5126
0002-7863
DOI: 10.1021/ja500090y
Popis: 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.
Databáze: OpenAIRE