General Method for the Amination of Aryl Halides with Primary and Secondary Alkyl Amines via Nickel Photocatalysis
General Method for the Amination of Aryl Halides with Primary and Secondary Alkyl Amines via Nickel Photocatalysis
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镍光催化伯烷基胺和仲烷基胺胺化芳基卤的通用方法
DOI：
10.1021/acs.joc.2c01284
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Dong Xue
中科院分区：
文献类型：
--
作者：
Geyang Song;Ding-Zhan Nong;Jing-Sheng Li;Gang Li;Wei Zhang;Rui Cao;Chao Wang;Jianliang Xiao;Dong Xue
Buchwald-Hartwig C-N偶联反应被列为药物化学中最常用的20个反应之一。由于镍基催化剂具有成本低、对氯代芳烃的反应活性高等优点，因此镍基催化剂在C-N偶联反应中的应用受到了广泛的关注。然而，迄今为止似乎没有通用的、实用的Ni催化体系能够使富电子和贫电子的芳基卤化物与伯烷基胺和仲烷基胺两者偶联。在这项研究中，据报道，镍（II）-联吡啶配合物催化有效的C-N耦合的芳基氯和溴与各种伯和仲烷基胺直接激发下与光。分子内的C-N耦合也被证明。200多个实例证明了该方法在有机合成中的可行性和适用性。
The Buchwald–Hartwig C–N coupling reaction has been ranked as one of the 20 most frequently used reactions in medicinal chemistry. Owing to its much lower cost and higher reactivity toward less reactive aryl chlorides than palladium, the C–N coupling reaction catalyzed by Ni-based catalysts has received a great deal of attention. However, there appear to be no universal, practical Ni catalytic systems so far that could enable the coupling of electron-rich and electron-poor aryl halides with both primary and secondary alkyl amines. In this study, it is reported that a Ni(II)-bipyridine complex catalyzes efficient C–N coupling of aryl chlorides and bromides with various primary and secondary alkyl amines under direct excitation with light. Intramolecular C–N coupling is also demonstrated. The feasibility and applicability of the protocol in organic synthesis is attested by more than 200 examples.