Aromatization modulates the activity of small organic molecules as promoters for carbon–halogen bond activation†,Chemical Science

当前位置： X-MOL 学术 › Chem. Sci. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Aromatization modulates the activity of small organic molecules as promoters for carbon–halogen bond activation†
Chemical Science ( IF 7.6 ) Pub Date : 2018-01-05 00:00:00 , DOI: 10.1039/c7sc04450j
Huan Yang ₁ , De-Zhao Chu ₁ , Lei Jiao ₁

Affiliation

The combination of small organic molecules and a base serves as a unique system for the activation carbon–halogen bonds in haloarenes by single electron transfer (SET). However, most of the molecules employed as promoters only allow for the activation of aryl iodides, and efficient activation of aryl bromides and chlorides under this mode is still rather challenging. Herein, we report the discovery of a structurally simple yet powerful promoter molecule, indoline, which exhibits unusually high activity in promoting the activation of haloarenes by SET. In the presence of t-BuOK and a trace amount of oxygen, indoline promotes the formation of aryl radicals not only from aryl iodides and bromides, but also from unactivated aryl chlorides (e.g., chlorobenzene) under relatively mild conditions. Mechanistic studies reveal the molecular basis for its high activity, for which the aromatization process plays a key role in modulating the electron transfer process.

中文翻译：

芳构化调节有机小分子的活性，作为碳-卤键活化的促进剂†

小有机分子和碱的组合作为通过单电子转移（SET）激活卤代芳烃中碳-卤素键的独特系统。然而，大多数用作促进剂的分子仅允许活化芳基碘化物，并且在这种模式下有效活化芳基溴化物和氯化物仍然相当具有挑战性。在此，我们报告发现了一种结构简单但功能强大的启动子分子二氢吲哚，它在促进 SET 活化卤代芳烃方面表现出异常高的活性。在t -BuOK和痕量氧存在下，二氢吲哚不仅促进芳基碘化物和芳基溴化物形成芳基自由基，而且还促进未活化的芳基氯化物(例如氯苯)在相对温和的条件下形成芳基自由基。机理研究揭示了其高活性的分子基础，其中芳构化过程在调节电子转移过程中起着关键作用。

更新日期：2018-01-05

点击分享查看原文

点击收藏

公开下载

阅读更多本刊最新论文本刊介绍/投稿指南11