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光氧化还原催化下以肟的衍生物作为前体亚胺自由基的产生及其反应

本站小编 Free考研考试/2022-02-14

摘要/Abstract



在可见光氧化还原催化的条件下,从肟的衍生物(O-酰基肟、O-芳基肟和α-亚胺氧杂酸等)出发,高效清洁地产生了亚胺自由基.这方法促进了亚胺自由基反应活性的系统研究.亚胺自由基主要有以下4种反应模式:(1)对芳烃的加成反应,(2)分子内的氢迁移,(3)对烯烃的加成反应,(4)Norrish-I型断裂(α-位的碳-碳键断裂)反应.综述了近几年来在光氧化还原催化的条件下,以肟的衍生物作为前体,亚胺自由基的产生及其参与的典型反应.
关键词: 氮自由基, 亚胺自由基, 光氧化还原催化, 可见光
The advent of visible light photoredox catalysis has transformed the way of single-electron transfer (SET) processes and accessing radical species. As a result, the chemistry of nitrogen-centered radicals has witnessed a remarkable gain in interest. Specifically, under visible light photoredox catalysis, iminyl radicals can be generated from oxime derivatives, such as O-acyl oximes, O-aryl oximes and α-imino-oxy acids. Meanwhile, the reactivity of iminyl radcials is investigated systematically. Iminyl radicals can undergo four major classes of reactions, namely addition to arenes, intramolecular hydrogen atom transfer and subsequent reactions, addition to alkenes, Norrish type-I fragmentation (cleavage of α-carbon-carbon bonds) and subsequent reactions. In this review, the most significant progresses in the use of oximes and their derivatives as iminyl precursors are discussed and their engagement in photoredox-mediated transformations is outlined.
Key words: nitrogen-centered radical, iminyl radical, photoredox catalysis, visible light


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相关话题/系统 亚胺 可见光 衍生物 条件下