关于受挫路易斯对催化的杂环烯 C-H 活化的密度泛函理论研究:电子效应对机理变化的调整

IF 1.9 4区 化学 Q2 CHEMISTRY, ORGANIC Journal of Physical Organic Chemistry Pub Date : 2024-07-22 DOI:10.1002/poc.4652
Youxiang Shao, Kang Xiao, Huize Wang, Yalan Liu
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引用次数: 0

摘要

非反应性 C-H 键活化是受挫路易斯对(FLPs)化学的一个新视野。虽然已有人提出了FLPs催化1-甲基吡咯C-H键活化的协同机理(Science 2015, 349, 513)和逐步碳化机理(Org. Lett.本研究采用密度泛函理论计算方法,研究了多种具有不同电子特性的 P-B 型 FLPs 催化 1-甲基吡咯的 C-H 键活化反应。详细的计算结果表明,FLPs 催化 C-H 活化的反应活性变化和反应机理二元化可以通过调整路易斯碱中心的电子效应来实现。一方面,协同 C-H 活化反应活性主要受路易斯碱中心孤对电子捐献的控制;因此,具有电子捐献取代基的 FLPs(FLP1、FLP2 和 FLP3)通过协同机制催化 C-H 键活化。另一方面,逐步碳化机制的反应活性主要归因于路易斯酸中心的空闲轨道,因此,带有 -P(C6F5)2 的 FLP5 更倾向于通过协同机制催化键的活化。相比之下,通过应变四元环过渡态的偏合成机制则不太可行。这些结果将为我们深入了解 FLPs 的结构和功能,合理设计 FLPs 催化 C-H 键活化提供更广阔的视角。
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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Density functional theory study on frustrated Lewis pairs catalyzed C-H activation of heteroarenes: Mechanism variation tuning by electronic effect

Unreactive C-H bond activation is a new horizon for frustrated Lewis pairs (FLPs) chemistry. Although concerted mechanism (Science 2015, 349, 513) and stepwise carbene mechanism (Org. Lett. 2018, 20, 1102) have been proposed for the FLPs catalyzed C-H bond activation of 1-methylpyrrole, the influence of electronic properties of FLPs on the reaction mechanism is far away from well-understood. In this study, an assortment of P-B type FLPs with different electronic characteristic was employed to study the catalyzed C-H bond activation of 1-methylpyrrole by using density functional theory calculations. Detailed calculations demonstrated that the reactivity variation and the reaction mechanism binary of FLPs catalyzed C-H activation can be varied by tuning electronic effect of Lewis base center. On the one hand, the concerted C-H activation reactivity is mainly controlled by the electron donation of the lone pair of Lewis base center; thus, the FLPs with electron-donating substituents (FLP1, FLP2, and FLP3) catalyzed the C-H bond activation through concerted mechanism. On the other hand, the reactivity of stepwise carbene mechanism is mostly attributed to the vacant orbital of Lewis acid center; as a result, the FLP5 bearing -P(C6F5)2 preferred to catalyzed the bond activation through concerted mechanism. In contrast, a metathesis mechanism through strained four-membered ring transition state is less feasible. These results should provide deeper insight and broader perspective to understand the structure and function of FLPs for rational design of FLPs catalyzed C-H bond activation.

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来源期刊
CiteScore
3.60
自引率
11.10%
发文量
161
审稿时长
2.3 months
期刊介绍: The Journal of Physical Organic Chemistry is the foremost international journal devoted to the relationship between molecular structure and chemical reactivity in organic systems. It publishes Research Articles, Reviews and Mini Reviews based on research striving to understand the principles governing chemical structures in relation to activity and transformation with physical and mathematical rigor, using results derived from experimental and computational methods. Physical Organic Chemistry is a central and fundamental field with multiple applications in fields such as molecular recognition, supramolecular chemistry, catalysis, photochemistry, biological and material sciences, nanotechnology and surface science.
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