过渡金属催化 CH 与氟化 π 系统官能化的实验与计算之旅

IF 20.3 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Coordination Chemistry Reviews Pub Date : 2024-09-24 DOI:10.1016/j.ccr.2024.216244

Zhongyi Zeng , Huiying Xu , Hui Gao, Zhi Zhou, Wei Yi

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引用次数: 0

摘要

利用不饱和碳氢化合物进行过渡金属催化的直接 CH 功能化已被确立为一种无需底物预功能化即可增加分子复杂性的可靠策略。特别是近年来，包括二氟炔烃、环丙烯和烯烃在内的几种创新氟化π体系的 CH 功能化模式得到了深入研究，不仅丰富了这一热点话题的新内涵，而且为如何促进过渡金属催化 CH 功能化与氟化学，甚至与药物科学的有机结合开辟了新的视野。在其固有的独特氟效应诱导下，这些氟官能化 π-化合物通过引入增强的化学选择性、区域选择性和立体选择性，有效地拓展了 CH 官能化反应的范围，极大地丰富了 CH 活化化学的内涵，并最终促进了有机化学的发展。在这篇综述中，我们全面总结了 2017 年以来过渡金属催化 CH 功能化与最新开发的氟化 π-体系的最新进展，尤其侧重于对反应发展的理性分析，以及通过计算研究与实验数据相结合揭示其机理。最后，还讨论了本课题面临的若干挑战和未来展望。我们相信，这篇综述能为实验和理论研究的协同结合提供深刻的见解，有助于未来设计由不同的 CH 活化底物和含氟 π 伙伴驱动的、尚未探索的 CH 功能化反应模式。这反过来又有望推动过渡金属催化 CH 活化/官能化领域创新反应范式的发现和发展。

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Experimental and computational journey on transition-metal-catalyzed CH functionalization with fluorinated π-systems

Transition-metal-catalyzed direct CH functionalization utilizing unsaturated hydrocarbons have been established as a robust strategy to increase molecular complexity without the need of substrate prefunctionalization. Especially, the CH functionalization mode involving several innovative fluorinated π-systems, including difluorinated alkynes, cyclopropenes as well as allenes, has been intensively investigated in recent years, which not only enriches the new connotation of this hot topic but also opens up a new field of vision on how to promote organic integration of transition-metal-catalyzed CH functionalization with fluorine chemistry, even with pharmaceutical science. Induced by their inherently distinctive fluorine effects, these fluorine-functionalized π-compounds have efficiently expanded the scope of the CH functionalization reactions by introducing enhanced chemoselectivity, regioselectivity and stereoselectivity, which greatly enriches the connotation of CH activation chemistry, and ultimately, promoting the development of organic chemistry. In this review, we provide a comprehensive summary of the latest progress in transition-metal-catalyzed CH functionalization with recently developed fluorinated π-systems since 2017, with particular focus on a rational analysis on reaction development and the elucidation of their mechanisms revealed by integrating computational investigation with experimental data. Finally, several challenges and future perspectives on this topic are also discussed. We believe that this review can offer a profound insight into the synergistic combination of experimental and theoretical studies for the future design of unexplored CH functionalization reaction modes driven by diverse CH activation substrates and fluorinated π-partners. This, in turn, is expected to spur the discovery and development of innovative reaction paradigms in this field of transition-metal-catalyzed CH activation/functionalization.

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来源期刊

Coordination Chemistry Reviews 化学-无机化学与核化学

CiteScore

34.30

自引率

5.30%

发文量

457

审稿时长

54 days

期刊介绍： Coordination Chemistry Reviews offers rapid publication of review articles on current and significant topics in coordination chemistry, encompassing organometallic, supramolecular, theoretical, and bioinorganic chemistry. It also covers catalysis, materials chemistry, and metal-organic frameworks from a coordination chemistry perspective. Reviews summarize recent developments or discuss specific techniques, welcoming contributions from both established and emerging researchers. The journal releases special issues on timely subjects, including those featuring contributions from specific regions or conferences. Occasional full-length book articles are also featured. Additionally, special volumes cover annual reviews of main group chemistry, transition metal group chemistry, and organometallic chemistry. These comprehensive reviews are vital resources for those engaged in coordination chemistry, further establishing Coordination Chemistry Reviews as a hub for insightful surveys in inorganic and physical inorganic chemistry.