Tertiary Alcohols as Radical Precursors for the Introduction of Tertiary Substituents into Heteroarenes
Tertiary Alcohols as Radical Precursors for the Introduction of Tertiary Substituents into Heteroarenes
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DOI：
10.1021/acscatal.9b00405
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发表时间：
2019-03
期刊：
影响因子：
12.9
通讯作者：
S. P. Pitre;Mikko Muuronen;D. Fishman;L. Overman
中科院分区：
文献类型：
--
作者：
S. P. Pitre;Mikko Muuronen;D. Fishman;L. Overman
尽管自Minisci及其同事的开创性报告以来，在缺电子杂芳烃的自由基烷基化方面取得了许多最新进展，但将叔烷基取代基直接掺入氮杂芳烃中的方法是有限的。本报告描述了使用叔烷基草酸盐，衍生自叔醇，引入叔取代基到各种杂环底物。该反应具有相当宽的范围，在温和的条件下快速进行，并且通过光化学或热活化引发。通过闪光光解研究获得了对高产可见光引发过程的潜在机制的见解，而计算研究提供了对反应范围的见解。
Despite many recent advances in the radical alkylation of electron-deficient heteroarenes since the seminal reports by Minisci and co-workers, methods for the direct incorporation of tertiary alkyl substituents into nitrogen heteroarenes are limited. This report describes the use of tert-alkyl oxalate salts, derived from tertiary alcohols, to introduce tertiary substituents into a variety of heterocyclic substrates. This reaction has reasonably broad scope, proceeds rapidly under mild conditions, and is initiated by either photochemical or thermal activation. Insights into the underlying mechanism of the higher yielding visible-light initiated process were obtained by flash photolysis studies, whereas computational studies provided insight into the reaction scope.