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 

机构地区：[1]School of Chemistry and Chemical Engineering,Southwest University

出　　处：《Chinese Chemical Letters》2015年第5期564-566,共3页中国化学快报（英文版）

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

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.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.

关 键 词：Trifluoromethylation Mechanism Density functional theory N-Heterocyclic carhene Trifluoromethyl copper complex 

分 类 号：O621.25[理学—有机化学]