Remote C-H Activation of Quinolines through Copper-Catalyzed Radical Cross-Coupling
Remote C-H Activation of Quinolines through Copper-Catalyzed Radical Cross-Coupling
复制标题
通过铜催化自由基交叉偶联远程 C-H 激活喹啉
DOI：
10.1002/asia.201501407
复制
发表时间：
2016
影响因子：
4.1
通讯作者：
Liu Xiaogang
中科院分区：
文献类型：
--
作者：
Xu Jun;Shen Chao;Zhu Xiaolei;Zhang Pengfei;Ajitha Manjaly J.;Huang Kuo-Wei Y.;An Zhongfu;Liu Xiaogang
在碳氢（C−H）官能化反应中实现位点选择性是有机化学中的一项艰巨挑战。在此，我们报告了一种在温和条件下通过铜催化磺酰化激活 8-氨基喹啉 C5 位远程 C-H 键的新方法。我们的策略显示出高转换效率、广泛的底物范围以及对不同官能团的良好耐受性。此外，我们的机理研究表明，单电子转移过程在生成磺酰基自由基以及随后引发 C−S 交叉偶联方面发挥着至关重要的作用。重要的是，我们的铜催化远程功能化协议可以扩展用于构建各种化学键，包括 C−O、C−Br、C−N、C−C 和 C−I。这些发现为远程 C−H 键的激活提供了基本的见解，同时为合理设计需要特定官能团修饰的药物分子和光电材料提供了新的可能性。
Achieving site selectivity in carbon–hydrogen (C−H) functionalization reactions is a formidable challenge in organic chemistry. Herein, we report a novel approach to activating remote C−H bonds at the C5 position of 8‐aminoquinoline through copper‐catalyzed sulfonylation under mild conditions. Our strategy shows high conversion efficiency, a broad substrate scope, and good toleration with different functional groups. Furthermore, our mechanistic investigations suggest that a single‐electron‐transfer process plays a vital role in generating sulfonyl radicals and subsequently initiating C−S cross‐coupling. Importantly, our copper‐catalyzed remote functionalization protocol can be expanded for the construction of a variety of chemical bonds, including C−O, C−Br, C−N, C−C, and C−I. These findings provide a fundamental insight into the activation of remote C−H bonds, while offering new possibilities for rational design of drug molecules and optoelectronic materials requiring specific modification of functional groups.