Reductive Amination by Photoredox Catalysis and Polarity-Matched Hydrogen Atom Transfer
Reductive Amination by Photoredox Catalysis and Polarity-Matched Hydrogen Atom Transfer
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DOI：
10.1002/anie.201711467
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发表时间：
2018-02-23
影响因子：
16.6
通讯作者：
Wenger, Oliver S.
中科院分区：
文献类型：
--
作者：
Guo, Xingwei;Wenger, Oliver S.
在抗坏血酸的存在下，Ru-II光敏剂的激发导致亚胺离子还原成富电子的α-氨基烷基自由基中间体，其通过硫醇介导的氢原子转移（HAT）迅速转化为还原性胺化产物。结果，通过光氧化还原催化的羰基化合物与胺的还原胺化以良好至优异的产率进行，并且具有宽的底物范围和良好的官能团耐受性。本工作的三个关键特征是1）在光氧化还原反应中通过极性匹配的HAT快速拦截富电子的α-氨基烷基自由基中间体，2）通过光氧化还原催化本身的还原胺化方法，和3）这种新方法在固体载体上的时间和空间控制反应的应用，如通过光氧化还原催化的还原胺化将荧光染料附着在活化的纤维素载体上所证明的。
The excitation of a Ru-II photosensitizer in the presence of ascorbic acid leads to the reduction of iminium ions to electron-rich alpha-aminoalkyl radical intermediates, which are rapidly converted into reductive amination products by thiol-mediated hydrogen atom transfer (HAT). As a result, the reductive amination of carbonyl compounds with amines by photoredox catalysis proceeds in good to excellent yields and with broad substrate scope and good functional group tolerance. The three key features of this work are 1)the rapid interception of electron-rich alpha-aminoalkyl radical intermediates by polarity-matched HAT in a photoredox reaction, 2)the method of reductive amination by photoredox catalysis itself, and 3)the application of this new method for temporally and spatially controlled reactions on a solid support, as demonstrated by the attachment of a fluorescent dye on an activated cellulose support by photoredox-catalyzed reductive amination.