Site-Selective Copper-Catalyzed Amination and Azidation of Arenes and Heteroarenes via Deprotonative Zincation,Journal of the American Chemical Society

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Site-Selective Copper-Catalyzed Amination and Azidation of Arenes and Heteroarenes via Deprotonative Zincation
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-08-14 00:00:00 , DOI: 10.1021/jacs.7b07661
Charles E. Hendrick ₁ , Katie J. Bitting ₁ , Seoyoung Cho ₁ , Qiu Wang ₁

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Arene amination is achieved by site-selective C–H zincation followed by copper-catalyzed coupling with O-benzoylhydroxylamines under mild conditions. Key to this success is ortho-zincation mediated by lithium amidodiethylzincate base that is effective for a wide range of arenes, including nonactivated arenes bearing simple functionalities such as fluoride, chloride, ester, amide, ether, nitrile, and trifluoromethyl groups as well as heteroarenes including indole, thiophene, pyridine, and isoquinoline. An analogous C–H azidation is also accomplished using azidoiodinane for direct introduction of a useful azide group onto a broad scope of arenes and heteroarenes. These new transformations offer rapid access to valuable and diverse chemical space of aminoarenes. Their broad applications in organic synthesis and drug discovery are demonstrated in the synthesis of novel analogues of natural product (−)-nicotine and antidepressant sertraline by late-stage amination and azidation reactions.

中文翻译：

通过去质子化锌对铜进行芳烃和杂芳烃的位点选择性铜催化胺化和叠氮化

芳烃的胺化反应是在温和的条件下，通过选择性的C–H锌化，然后与O-苯甲酰羟胺进行铜催化偶联而实现的。成功的关键是邻由氨基二乙基锌酸锂碱介导的β-锌化，可有效用于多种芳烃，包括具有简单功能的非活化芳烃，例如氟化物，氯，酯，酰胺，醚，腈和三氟甲基；以及杂芳烃，包括吲哚，噻吩，吡啶和异喹啉。还可以使用叠氮碘烷将类似的CH叠氮化，将有用的叠氮化物基团直接引入广泛的芳烃和杂芳烃中。这些新的转变提供了快速进入氨基芳烃宝贵而多样的化学空间的途径。通过后期胺化和叠氮化反应合成天然产物（-）-尼古丁和抗抑郁剂舍曲林的新型类似物，证明了它们在有机合成和药物开发中的广泛应用。

更新日期：2017-08-14

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