在亚胺和乙烯基乙酸的辅助下,钯催化芳基胺的正交-C(sp2)-H 活化/环化。

IF 14.7 1区 综合性期刊 Q1 MULTIDISCIPLINARY SCIENCES Nature Communications Pub Date : 2024-11-14 DOI:10.1038/s41467-024-54018-2
Xiangwen Tan, Yaru Jing, Jiahao Wu, Jiatian Li, Zhenjie Yang, Wanqing Wu, Zhuofeng Ke, Huanfeng Jiang
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引用次数: 0

摘要

钯催化定向 C-H 功能化/环化是合成氮杂环的有效方法。亚胺因其易于安装/拆卸而闻名,已被广泛用于醛、酮和烷基胺的 C-H 活化。然而,在芳基胺的 C(sp2)-H 活化中,由于会产生一个紧张的四元偶氮杂环,因此很少有人对其进行研究。在此,我们建立了一种在乙烯基乙酸辅助下由亚胺引导的钯催化芳基胺的 C(sp2)-H 功能化方法,从而在温和的反应条件下获得了多种γ-内酯融合的四氢喹啉。该方法具有广泛的底物范围和良好的官能团耐受性,是有机合成领域的显著进步。机理实验阐明了 C(sp2)-H活化是如何发生的,表明了乙烯基乙酸的关键作用。DFT 计算支持了观察结果,阐明了乙烯基乙酸的配位和氢键相互作用克服了紧张的四元环 C-H 活化障碍。
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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Palladium catalyzed ortho-C(sp2)-H activation/cyclization of aryl amines assisted by imine and vinylacetic acid.

Palladium-catalyzed directed C - H functionalization/cyclization is an effective approach for synthesizing nitrogen heterocycles. Imine, known for its ease of installation/removal, has been extensively used in the C-H activation of aldehydes, ketones, and alkylamines. Nevertheless, it has been rarely explored in the C(sp2)-H activation of aryl amines because of the generation of a strained four-membered palladacycle. Herein, an imine directed palladium catalyzed C(sp2)-H functionalization of aryl amines assisted by vinylacetic acid is established, providing access to a variety of γ-lactone fused tetrahydroquinolines under mild reaction conditions. The methodology demonstrates broad substrate scope and good functional group tolerance, representing notable advancement in organic synthesis. Mechanistic experiments are performed to clarify how the C(sp2)-H activation occurs, indicating the crucial role of vinylacetic acid. DFT calculations supports the observations, elucidating the strained four-membered ring C-H activation barrier is overcome via coordination and hydrogen bond interaction of vinylacetic acid.

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来源期刊
Nature Communications
Nature Communications Biological Science Disciplines-
CiteScore
24.90
自引率
2.40%
发文量
6928
审稿时长
3.7 months
期刊介绍: Nature Communications, an open-access journal, publishes high-quality research spanning all areas of the natural sciences. Papers featured in the journal showcase significant advances relevant to specialists in each respective field. With a 2-year impact factor of 16.6 (2022) and a median time of 8 days from submission to the first editorial decision, Nature Communications is committed to rapid dissemination of research findings. As a multidisciplinary journal, it welcomes contributions from biological, health, physical, chemical, Earth, social, mathematical, applied, and engineering sciences, aiming to highlight important breakthroughs within each domain.
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