Privileged Phosphine-Based Metal鈥揙rganic Frameworks for Broad-Scope Asymmetric Catalysis
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- 作者：Joseph M. Falkowski ; Takahiro Sawano ; Teng Zhang ; Galen Tsun ; Yuan Chen ; Jenny V. Lockard ; Wenbin Lin
- 刊名：Journal of the American Chemical Society
- 出版年：2014
- 出版时间：April 9, 2014
- 年：2014
- 卷：136
- 期：14
- 页码：5213-5216
- 全文大小：296K
- 年卷期：v.136,no.14(April 9, 2014)
- ISSN：1520-5126
文摘
A robust and porous Zr metal鈥搊rganic 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 伪,尾-unsaturated ketones and hydrogenation of substituted alkene and carbonyl compounds.