Mechanism of trifluoromethylation reactions with well-defined NHC copper trifluoromethyl complexes and iodobenzene:A computational exploration

作     者：Dong-Hai Yu Jing-Na Shao Rong-Xing He Ming Li 

作者机构：School of Chemistry and Chemical EngineeringSouthwest University 

出 版 物：《Chinese Chemical Letters》 (中国化学快报（英文版）)

年 卷 期：2015年第26卷第5期

页      面：564-566页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：supported by National Natural Science Foundation of China(Nos.21073144,21173169) Fundamental Research Funds for the Central Universities(No.XDJK2013A008) 

主　　题：Trifluoromethylation Mechanism Density functional theory N Heterocyclic carhene Trifluoromethyl copper complex 

摘      要：Computational calculation was performed to investigate the mechanism of trifluoromethylation reactions of iodobenzene with well-defined N-heterocyclic carbene （NHC）-supported Cu~ trifiuor- omethyl complexes. Four proposed reaction pathways, namely cr-bond metathesis （BM）, concerted oxidative addition-reductive elimination （OARE）, iodine atom transfer （IAT） and single-electron transfer （SET）, have been computed by density functional theory （DFT）. The result indicated that the concerted OARE mechanism is favored among the four reaction pathways, suggesting the trifluoromethylation may occur via concerted OARE mechanism involving Ar-X oxidative addition to the Cu（1） center as the rate determining step.