Liang Kang, Zhang Qinglin, Guo Chang
Hefei National Research Center for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, Hefei 230026, China.
Sci Adv. 2022 Nov 11;8(45):eadd7134. doi: 10.1126/sciadv.add7134. Epub 2022 Nov 9.
The development of general electrocatalytic methods for the diversity-oriented regio- and stereoselective functionalization of alkenes remains a challenge in organic synthesis. We present a switchable electrocatalytic method based on anodic oxidative activation for the controlled liberation of chiral α-keto radical species toward stereoselective organic transformations. Electrogenerated α-keto radical species capture alkene partners, allowing switchable intermolecular alkene difunctionalization and alkenylation in a highly stereoselective manner. In addition to acting as proton donors to facilitate H evolution at the cathode, the unique properties of alcohol additives play an important role in determining the distinct outcomes for alkene functionalization under electrocatalytic conditions.
开发用于烯烃区域和立体选择性官能团化的通用电催化方法仍然是有机合成中的一个挑战。我们提出了一种基于阳极氧化活化的可切换电催化方法，用于可控释放手性α-酮基自由基物种以实现立体选择性有机转化。电生成的α-酮基自由基物种捕获烯烃底物，从而以高度立体选择性的方式实现可切换的分子间烯烃双官能团化和烯基化。除了作为质子供体促进阴极析氢外，醇添加剂的独特性质在决定电催化条件下烯烃官能团化的不同结果方面起着重要作用。
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