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有机介导的电化学转化

Organo-mediator enabled electrochemical transformations.

作者信息

Zeng Weimei, Wang Yanwei, Peng Chengyi, Qiu Youai

机构信息

State Key Laboratory and Institute of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, Haihe Laboratory of Sustainable Chemical Transformations, College of Chemistry, Nankai University, 94 Weijin Road, Tianjin 300071, China.

出版信息

Chem Soc Rev. 2025 May 6;54(9):4468-4501. doi: 10.1039/d4cs01142b.

Abstract

Electrochemistry has emerged as a powerful means to facilitate redox transformations in modern chemical synthesis. This review focuses on organo-mediators that facilitate electrochemical reactions outer-sphere electron transfer (ET) between active mediators and substrates, offering advantages over direct electrolysis due to their availability, ease of modification, and simple post-processing. They prevent overoxidation/reduction, enhance selectivity, and mitigate electrode passivation during the electrosynthesis. By modifying the structure of organo-mediators, those with tunable redox potentials enable electrosynthesis and avoid metal residues in the final products, making them promising for further application in synthetic chemistry, particularly in pharmacochemistry, where the maximum allowed level of the metal residue in synthetic samples is extremely strict. This review highlights the recent advancements in this rapidly growing area within the past two decades, including the electrochemical organo-mediated oxidation (EOMO) and electrochemical organo-mediated reduction (EOMR) events. The organo-mediator enabled electrochemical transformations are discussed according to the reaction type, which has been categorized into oxidation and reduction organic mediators.

摘要

电化学已成为现代化学合成中促进氧化还原转化的有力手段。本综述聚焦于促进电化学反应的有机介质,即活性介质与底物之间的外层电子转移(ET),因其可用性、易于修饰和后处理简单,相较于直接电解具有优势。它们可防止过度氧化/还原,提高选择性,并减轻电合成过程中的电极钝化。通过修饰有机介质的结构,具有可调氧化还原电位的介质能够实现电合成并避免最终产物中出现金属残留,这使其在合成化学,尤其是药物化学中具有广阔的应用前景,因为合成样品中金属残留的最大允许水平极为严格。本综述重点介绍了过去二十年来这一快速发展领域的最新进展,包括电化学有机介导氧化(EOMO)和电化学有机介导还原(EOMR)事件。根据反应类型对有机介质介导的电化学转化进行了讨论,反应类型已分为氧化型和还原型有机介质。

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