Photoinduced Ullmann C-N Coupling: Demonstrating the Viability of a Radical Pathway
Photoinduced Ullmann C-N Coupling: Demonstrating the Viability of a Radical Pathway
复制标题
DOI：
10.1126/science.1226458
复制
发表时间：
2012-11-02
期刊：
影响因子：
56.9
通讯作者：
Peters, Jonas C.
中科院分区：
文献类型：
--
作者：
Creutz, Sidney E.;Lotito, Kenneth J.;Peters, Jonas C.
胺与芳基卤化物在高温（>180 ℃）下通过化学计量的铜试剂介导的碳-氮（C-N）键形成反应生成芳基胺（苯胺），首先由Ullmann在1903年描述。在其后的世纪，这种和相关的C-N键形成过程已经成为有机合成的有力工具。在这里，我们报告说，Ullmann C-N耦合可以通过使用化学计量或催化量的铜来光诱导，这使得反应能够在异常温和的条件下（室温甚至-40 ℃）进行。一系列的数据是一致的单电子转移机制，代表了最实质性的实验支持到目前为止的可行性，这一途径的Ullmann C-N耦合。
Carbon-nitrogen (C-N) bond-forming reactions of amines with aryl halides to generate arylamines (anilines), mediated by a stoichiometric copper reagent at elevated temperature (>180 degrees C), were first described by Ullmann in 1903. In the intervening century, this and related C-N bond-forming processes have emerged as powerful tools for organic synthesis. Here, we report that Ullmann C-N coupling can be photoinduced by using a stoichiometric or a catalytic amount of copper, which enables the reaction to proceed under unusually mild conditions (room temperature or even -40 degrees C). An array of data are consistent with a single-electron transfer mechanism, representing the most substantial experimental support to date for the viability of this pathway for Ullmann C-N couplings.