Light-Promoted C-N Coupling of Aryl Halides with Nitroarenes
Light-Promoted C-N Coupling of Aryl Halides with Nitroarenes
复制标题
芳基卤化物与硝基芳烃的光促进 C–N 偶联
DOI：
10.1002/anie.202012877
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发表时间：
2021-01-18
影响因子：
16.6
通讯作者：
Xue, Dong
中科院分区：
文献类型：
--
作者：
Li, Gang;Yang, Liu;Xue, Dong
首次展示了芳基卤化物与硝基芳烃的光化学C - N偶联反应。在没有任何外部光敏剂的情况下，由镍（II）配合物催化，容易获得的硝基芳烃与多种芳基卤化物发生偶联，为广泛使用的布赫瓦尔德 - 哈特维希C - N偶联反应提供了一种步骤经济的扩展。该方法对具有空间位阻以及对碱和亲核试剂敏感的官能团的偶联底物具有耐受性。机理研究表明，反应是通过由镍（I）/镍（III）循环产生的芳基自由基加成到亚硝基芳烃中间体上进行的。
A photochemical C-N coupling of aryl halides with nitroarenes is demonstrated for the first time. Catalyzed by a Ni-II complex in the absence of any external photosensitizer, readily available nitroarenes undergo coupling with a variety of aryl halides, providing a step-economic extension to the widely used Buchwald-Hartwig C-N coupling reaction. The method tolerates coupling partners with steric-congestion and functional groups sensitive to bases and nucleophiles. Mechanistic studies suggest that the reaction proceeds via the addition of an aryl radical, generated from a Ni-I/Ni-III cycle, to a nitrosoarene intermediate.