Mn-Catalyzed Electrochemical Chloroalkylation of Alkenes
Mn-Catalyzed Electrochemical Chloroalkylation of Alkenes
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DOI：
10.1021/acscatal.8b03209
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发表时间：
2019-01-01
期刊：
影响因子：
12.9
通讯作者：
Lin, Song
中科院分区：
文献类型：
--
作者：
Fu, Niankai;Shen, Yifan;Lin, Song
烯烃的异双官能化是合成高官能化有机分子的有效方法。在本报告中，我们描述了使用阳极耦合电解从丙二腈或氰乙酸盐和 NaCl 催化烯烃氯烷基化，这是一种在单一合成操作中构建邻位 C-C 和 C-Cl 键的反应。对持久自由基效应的了解指导了反应的设计和开发。一系列受控实验，包括划分阳极和阴极事件的分室电解，使我们能够确定关键的自由基中间体及其电催化形成的途径。循环伏安数据进一步支持了所提出的机制，该机制需要在阳极耦合电解中并行地、Mn介导地生成两种自由基中间体，然后将它们选择性地添加到烯烃中。
The heterodifunctionalization of alkenes is an efficient method for synthesizing highly functionalized organic molecules. In this report, we describe the use of anodically coupled electrolysis for the catalytic chloroalkylation of alkenes-a reaction that constructs vicinal C-C and C-Cl bonds in a single synthetic operation-from malononitriles or cyanoacetates and NaCl. Knowledge of the persistent radical effect guided the reaction design and development. A series of controlled experiments, including divided-cell electrolysis that compartmentalized the anodic and cathodic events, allowed us to identify the key radical intermediates and the pathway to their electrocatalytic formation. Cyclic voltammetry data further support the proposed mechanism entailing the parallel, Mn-mediated generation of two radical intermediates in an anodically coupled electrolysis followed by their selective addition to the alkene.