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以水为氢源对未活化烯烃进行电还原反应。

Electroreduction of unactivated alkenes using water as hydrogen source.

作者信息

Wang Yanwei, Wang Qian, Wu Lei, Jia Kangping, Wang Minyan, Qiu Youai

机构信息

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

State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China.

出版信息

Nat Commun. 2024 Mar 30;15(1):2780. doi: 10.1038/s41467-024-47168-w.

Abstract

Herein, we report an electroreduction of unactivated alkyl alkenes enabled by [Fe]-H, which is provided through the combination of anodic iron salts and the silane generated in situ via cathodic reduction, using HO as an H-source. The catalytic amounts of Si-additive work as an H-carrier from HO to generate a highly active silane species in situ under continuous electrochemical conditions. This approach shows a broad substrate scope and good functional group compatibility. In addition to hydrogenation, the use of DO instead of HO provides the desired deuterated products in good yields with excellent D-incorporation (up to >99%). Further late-stage hydrogenation of complex molecules and drug derivatives demonstrate potential application in the pharmaceutical industry. Mechanistic studies are performed and provide support for the proposed mechanistic pathway.

摘要

在此,我们报道了一种由[Fe]-H实现的未活化烷基烯烃的电还原反应,[Fe]-H是通过阳极铁盐与阴极还原原位生成的硅烷相结合,并以HO作为氢源提供的。催化量的硅添加剂作为从HO来的氢载体,在连续电化学条件下原位生成高活性硅烷物种。该方法显示出广泛的底物范围和良好的官能团兼容性。除氢化反应外,使用DO代替HO可提供所需的氘代产物,产率良好,氘掺入率极高(高达>99%)。复杂分子和药物衍生物的进一步后期氢化反应证明了其在制药工业中的潜在应用。进行了机理研究,并为所提出的机理途径提供了支持。

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