Radical-Radical Cross-Coupling for C-S Bond Formation
Radical-Radical Cross-Coupling for C-S Bond Formation
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DOI：
10.1021/acs.orglett.6b00764
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发表时间：
2016-05-20
期刊：
影响因子：
5.2
通讯作者：
Lei, Aiwen
中科院分区：
文献类型：
--
作者：
Huang, Zhiliang;Zhang, Dongchao;Lei, Aiwen
提出了一种新的方法来克服自由基交叉偶联反应在合成不对称二芳基硫醚中的选择性问题。通过自由基捕获实验、密度泛函理论计算和动力学等方法，初步揭示了反应机理，表明C-S键通过硫代自由基和芳基自由基阳离子的交叉偶联形成。此外，取代C-H键断裂的芳基自由基阳离子的形成被确定为限速步骤。
A new method was demonstrated to overcome the selectivity issue of radical radical cross-coupling toward the synthesis of asymmetric diaryl thioethers. The preliminary mechanism was revealed by radical-trapping experiments, DFT calculations, and kinetics, etc., indicating that the C-S bond formed through cross-coupling of a thiyl radical and an aryl radical cation. Moreover, the formation of an aryl radical cation instead of the C-H bond cleavage was determined as the rate-limiting step.