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碳键金属催化(CBMC):超分子复合物在金催化反应中指导结构异构体的选择。

Carbon-Bonding Metal Catalysis (CBMC): A Supramolecular Complex Directs Structural-Isomer Selection in Gold-Catalyzed Reactions.

作者信息

Li Xinxin, Hu Lingfei, Lu Gang, Wang Yao

机构信息

School of Chemistry and Chemical Engineering, Key Laboratory of Colloid and Interface Chemistry of the Ministry of Education, Shandong University, Jinan 250100, P. R. China.

出版信息

J Am Chem Soc. 2023 Oct 4;145(39):21554-21561. doi: 10.1021/jacs.3c07551. Epub 2023 Sep 5.

DOI:10.1021/jacs.3c07551
PMID:37668596
Abstract

Carbon is a primary element to constitute organic molecules, while metal catalysis is a basic tool in organic synthesis. The establishment of a link between the ubiquitous carbon bonding and metal catalysis is thus a fundamentally important problem. However, there is yet no experimental example to introduce the role of carbon bonding in a metal catalysis process. Herein, we merged the topics of carbon bonding and metal catalysis together and demonstrated that a supramolecular carbon-bonding metal complex can not only give rise to catalytic activity but, more remarkably, direct structural-isomer selection events in gold-catalyzed reactions. The experimental results unveil the fact that the imposing of weak carbon-bonding interactions on a gold complex can alter the carbene as well as the Lewis acid property of these catalysts. These results illustrate a non-negligible role of weak carbon-bonding interactions in the modulation of metal catalysis. As such, carbon-bonding metal catalysis is suggested to be used as a routine tool not only in the development of reactions but more frequently in analyzing reaction processes in metal catalysis.

摘要

碳是构成有机分子的主要元素,而金属催化是有机合成中的基本工具。因此,在无处不在的碳键合与金属催化之间建立联系是一个至关重要的基本问题。然而,目前尚无实验实例来介绍碳键合在金属催化过程中的作用。在此,我们将碳键合和金属催化这两个主题结合在一起,证明了一种超分子碳键合金属配合物不仅能产生催化活性,更显著的是,能在金催化反应中引导结构异构体的选择事件。实验结果揭示了一个事实,即在金配合物上施加弱碳键相互作用可以改变这些催化剂的卡宾以及路易斯酸性质。这些结果说明了弱碳键相互作用在金属催化调节中不可忽视的作用。因此,建议将碳键合金属催化不仅用作反应开发中的常规工具,更频繁地用于分析金属催化中的反应过程。

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