BINAP-Functionalized 2D Metal-Organic Frameworks for Heterogeneous Rh Catalysts

IF 2.5 4区化学 Q3 CHEMISTRY, PHYSICAL

Catalysis Letters Pub Date : 2026-09-23 DOI:10.1007/s10562-026-05528-9

Xiao Feng, Chengzhong Huang, Baogang Yang, Yanling Han

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Abstract

Two-dimensional metal organic frameworks (2D MOFs), characterized by their atomic-level thickness, ultrahigh specific surface area, and highly exposed active sites, offer an ideal platform for constructing advanced heterogeneous catalysts. Herein, chiral BINAP-derived ligands were successfully immobilized within a 2D MOF scaffold, followed by metallization with rhodium (Rh) active species to construct a well-defined heterogeneous asymmetric catalyst. The obtained Zr-BTB-L-Rh retained the intact hierarchical porous structure with atomically dispersed Rh active species, providing an excellent “quasi-homogeneous” environment for efficient reactant transport. In the asymmetric Hayashi-Miyaura addition of arylboronic acids to 2-cyclohexen-1-one, the catalyst demonstrated exceptional performance with over 99% yield and over 99% enantioselectivity (ee). Remarkably, it enabled a turnover number (TON) up to 99 times that of its homogeneous counterpart at low catalyst loading. Moreover, the catalyst could be easily recycled and maintains stable activity and enantioselectivity over five consecutive runs.

Graphical Abstract

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非均相Rh催化剂的binap功能化二维金属有机骨架

二维金属有机骨架（2D MOFs）具有原子级厚度、超高比表面积和高度暴露的活性位点等特点，为构建先进的非均相催化剂提供了理想的平台。本文中，手性binap衍生的配体成功地固定在二维MOF支架内，然后与铑（Rh）活性物质进行金属化，构建了一个定义良好的非均质不对称催化剂。得到的Zr-BTB-L-Rh保留了完整的分层多孔结构，具有原子分散的Rh活性物质，为有效的反应物传输提供了良好的“准均匀”环境。在Hayashi-Miyaura催化芳基硼酸与2-环己烯-1- 1的不对称加成反应中，催化剂表现出99%以上的收率和99%以上的对映选择性（ee）。值得注意的是，在低催化剂负载下，它使周转率（TON）达到均匀对应物的99倍。此外，该催化剂易于回收，并且在连续五次运行中保持稳定的活性和对映体选择性。图形抽象

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Catalysis Letters 化学-物理化学

CiteScore

5.70

自引率

3.60%

发文量

327

审稿时长

1 months

期刊介绍： Catalysis Letters aim is the rapid publication of outstanding and high-impact original research articles in catalysis. The scope of the journal covers a broad range of topics in all fields of both applied and theoretical catalysis, including heterogeneous, homogeneous and biocatalysis. The high-quality original research articles published in Catalysis Letters are subject to rigorous peer review. Accepted papers are published online first and subsequently in print issues. All contributions must include a graphical abstract. Manuscripts should be written in English and the responsibility lies with the authors to ensure that they are grammatically and linguistically correct. Authors for whom English is not the working language are encouraged to consider using a professional language-editing service before submitting their manuscripts.