Theoretical study on the reaction mechanism of Pd(OAc)2-catalyzed trifluoroethylation: Role of additive CF3COOH |
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| Authors: | Dimao Wen Binfang Yuan Rongxing He Wei Shen Ming Li |
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| Institution: | 1. Key Laboratory of Luminescence and Real-Time Analytical Chemistry (Southwest University), Ministry of Education, College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, China;2. Department of Chemistry and Chemical Engineering, Yangtze Normal University, Chongqing, Fuling 408100, China |
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| Abstract: | The mechanism of Pd(OAc)2-catalyzed trifluoroethylation of aromatic systems is explored using the density function theory (DFT) computations. The calculation results indicate that the whole catalytic cycle involves a coordinated process of catalyst Pd(OAc)2 with acetanilide 1a, a C–H bond activation and a two-step migration of CF3CH2– group. The interesting role of additive (CF3COOH) is that it can react with substrate 2a (mesityl(trifluoroethyl)iodonium triflate) to form an active species mesityl(trifluoroethyl)iodonium trifluoroacetate 2a′. 2a′ can assist the C–H activation to decrease the rate-limiting free energy barrier of the catalytic reaction by changing the rate-limiting step from the transferring process of CF3CH2– group to the C–H bond activation. |
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| Keywords: | DFT Additive Trifluoroethylation |
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