Citation: Dong-Hai Yu, Jing-Na Shao, Rong-Xing He, Ming Li. Mechanism of trifl uoromethylation reactions with well-defi ned NHC copper trifl uoromethyl complexes and iodobenzene: A computational exploration[J]. Chinese Chemical Letters, ;2015, 26(5): 564-566. doi: 10.1016/j.cclet.2014.12.017 shu

Mechanism of trifl uoromethylation reactions with well-defi ned NHC copper trifl uoromethyl complexes and iodobenzene: A computational exploration

1.
School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, China

Corresponding author: Ming Li,
Received Date: 30 September 2014
Available Online: 8 December 2014
Fund Project: This work was supported by National Natural Science Foundation of China (Nos. 21073144, 21173169) (Nos. 21073144, 21173169)the Fundamental Research Funds for the Central Universities (No. XDJK2013A008). Computing resources were provided by the National Supercomputing Center of China in Shenzhen. (No. XDJK2013A008)

Computational calculation was performed to investigate the mechanism of trifluoromethylation reactions of iodobenzene with well-defined N-heterocyclic carbene (NHC)-supported Cu^I trifluoromethyl complexes. Four proposed reaction pathways, namely σ-bond metathesis (BM), concerted oxidative addition-reductive elimination (OARE), iodine atomtransfer (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(I) center as the rate determining step.
- Trifluoromethylation,
- Mechanism,
- Density functional theory,
- N-Heterocyclic carbene,
- Trifluoromethyl copper complex
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