戴维斯-贝鲁特反应：一种光化学布朗斯特酸催化的 -芳基 2-吲哚合成方法。
Davis-Beirut Reaction: A Photochemical Brønsted Acid Catalyzed Route to -Aryl 2-Indazoles.
机构信息
Department of Chemistry , University of California Davis , 1 Shields Avenue , Davis , California 95616 , United States.
Department of Chemistry , American University of Beirut , Beirut , Lebanon.
出版信息
Org Lett. 2019 Aug 2;21(15):6058-6062. doi: 10.1021/acs.orglett.9b02213. Epub 2019 Jul 24.
Abstract
The Davis-Beirut reaction provides access to 2-indazoles from aromatic nitro compounds. However, -aryl targets have been traditionally challenging to access due to competitive alternate reaction pathways. Previously, the key nitroso imine intermediate was generated under alkaline conditions, but as reported here, the photochemistry of -nitrobenzyl alcohols empowered Brønsted acid catalyzed conditions for accessing -aryl targets. Anilines and alkyl amines give different outcomes under optimized conditions; the proposed mechanism was studied using quantum chemical calculations.
摘要
戴维斯-贝鲁特反应为芳香族硝基化合物提供了 2-吲唑的合成途径。然而，由于竞争性的替代反应途径，-芳基目标物传统上难以获得。以前，关键的亚硝基亚胺中间体是在碱性条件下生成的，但正如这里所报道的，-硝基苄醇的光化学为 Brønsted 酸催化条件下获得-芳基目标物提供了支持。优化条件下苯胺和烷基胺会产生不同的结果；使用量子化学计算研究了提出的反应机制。
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