通过可见光光催化和路易斯酸催化协同作用实现无还原剂对映体选择性氮杂-变形反应

IF 16.9 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Angewandte Chemie International Edition Pub Date : 2025-02-18 DOI:10.1002/anie.202500756
Mingyi Jiang, Zengcheng Yu, Linhan Yang, Prof. Fei Wang, Prof. Weidi Cao, Prof. Xiaohua Liu, Prof. Xiaoming Feng
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引用次数: 0

摘要

经典的aza-Reformatsky反应通常涉及过量的还原剂。在此,我们开发了一个可见光诱导的不对称aza-Reformatsky反应,通过手性Lewis酸辅助直接激发亚胺而不添加还原剂,使碘二氟甲基酮的碳-碘键断裂和随后的对映选择性自由基偶联。该方案提供了一个巧妙的途径,手性β-氨基酮含有宝石二氟基团。自由基俘获实验、电子顺磁共振实验、循环伏安实验和光谱分析等机理研究使反应过程合理化。
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Reductant-Free Enantioselective Aza-Reformatsky Reaction Enabled by Synergistic Visible Light Photocatalysis and Lewis Acid Catalysis

Classical aza-Reformatsky reaction generally involves excess reductants. Herein, we developed a visible light-induced catalytic asymmetric aza-Reformatsky reaction via a chiral Lewis acid-assisted direct excitation of imines without additional reductants, enabling the carbon–iodine bond cleavage of iododifluoromethyl ketones and the subsequent enantioselective radical coupling. This protocol provided an ingenious access to chiral β-amino ketones containing a gem-difluorine moiety. The mechanistic studies including radical trapping experiment, NMR experiment, electron paramagnetic resonance experiment, cyclic voltammetry experiment and spectroscopic analysis rationalized the reaction process.

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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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