Copper-catalyzed oxidative benzylic C-H cyclization via iminyl radical from intermolecular anion-radical redox relay.,Nature Communications

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Copper-catalyzed oxidative benzylic C-H cyclization via iminyl radical from intermolecular anion-radical redox relay.
Nature Communications ( IF 14.7 ) Pub Date : 2019-02-22 , DOI: 10.1038/s41467-019-08849-z
Xiang-Huan Shan ₁ , Hong-Xing Zheng ₁ , Bo Yang ₁ , Lin Tie ₁ , Jia-Le Fu ₁ , Jian-Ping Qu ₂ , Yan-Biao Kang ₁

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Base-promoted C-H cleavage without transition metals opens a practical alternative for the one based on noble metals or radical initiators. The resulting carbanion can pass through radical addition to unsaturated bonds like C-N or C-C triple bonds, in which stoichiometric oxidants are needed. When in situ C-H cleavage meets catalytic carbanion-radical relay, it turns to be challenging but has not been accomplished yet. Here we report the combination of base-promoted benzylic C-H cleavage and copper-catalyzed carbanion-radical redox relay. Catalytic amount of naturally abundant and inexpensive copper salt, such as copper(II) sulfate, is used for anion-radical redox relay without any external oxidant. By avoiding using N-O/N-N homolysis or radical initiators to generate iminyl radicals, this strategy realizes modular synthesis of N-H indoles and analogs from abundant feedstocks, such as toluene and nitrile derivatives, and also enables rapid synthesis of large scale pharmaceuticals.

中文翻译：

铜催化的分子间阴离子-自由基氧化还原中继反应中亚胺基的氧化苄基CH环化反应。

不含过渡金属的碱促进的CH裂解为基于贵金属或自由基引发剂的CH裂解开辟了一种实用的替代方法。产生的碳负离子可以通过自由基加成至不饱和键（如CN或CC三键），其中需要化学计量的氧化剂。当原位CH裂解遇到催化碳负离子自由基中继时，这具有挑战性，但尚未完成。在这里，我们报告了碱促进的苄基CH裂解和铜催化的碳负离子自由基氧化还原中继的结合。催化量的天然丰富且廉价的铜盐，例如硫酸铜（II），用于阴离子自由基氧化还原中继，而无需任何外部氧化剂。通过避免使用NO / NN均质分解或自由基引发剂生成亚氨基自由基，

更新日期：2019-02-22

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