不对称反阴离子定向电催化技术用于对立选择性控制自由基阳离子。

IF 16.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Angewandte Chemie International Edition Pub Date : 2024-08-29 DOI:10.1002/anie.202413601
Zhenhui Xu, Changdi Zheng, Jie Lin, Weiwei Huang, Dingguo Song, Weihui Zhong, Fei Ling
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引用次数: 0

摘要

尽管有一些成功的例子,但控制自由基阳离子反应中的对映选择性是一项长期的挑战。我们介绍了一种不对称反阴离子定向电催化的新策略,以解决自由基阳离子化学中的对映选择性问题。这一概念已在两个反应中得到了成功验证:不对称脱氢吲哚-苯酚 [3 + 2] 偶联和异选择性 C-H/N-H 脱氢偶联。这些反应使得苯并呋喃吲哚和 C-N 轴手性吲哚的合成成为可能,而且产量高,对映体过量。详细的机理研究证实了自由基-自由基耦合机理。此外,密度泛函理论(DFT)计算支持吲哚自由基阳离子作为关键中间体,而不是中性吲哚自由基,这为揭示驱动这些反应的基本过程提供了新的线索。
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Asymmetric Counteranion-Directed Electrocatalysis for Enantioselective Control of Radical Cation.

The control of enantioselectivity in radical cation reactions presents long-standing challenges, despite a few successful examples. We introduce a novel strategy of asymmetric counteranion-directed electrocatalysis to address enantioselectivity in radical cation chemistry. This concept has been successfully demonstrated in two reactions: an asymmetric dehydrogenative indole-phenol [3+2] coupling and an atroposelective C-H/N-H dehydrogenative coupling. These reactions have enabled the synthesis of benzofuroindolines and C-N axially chiral indoles with high yields and excellent enantiomeric excesses. Detailed mechanistic studies confirmed a radical-radical coupling mechanism. Moreover, density functional theory (DFT) calculations supported the indole radical cation as the pivotal intermediate, rather than a neutral indolyl radical, shedding new light on the underlying processes driving these reactions.

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来源期刊
CiteScore
26.60
自引率
6.60%
发文量
3549
审稿时长
1.5 months
期刊介绍: Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.
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