Citation: Wang Wei, Mao Shuang, Peng Dan, Li Laicai. Investigation on the Mechanism for N-Methylindole and Keto Ester Catalyzed by InX₃ (X=F, Br)[J]. Chinese Journal of Organic Chemistry, ;2016, 36(3): 613-621. doi: 10.6023/cjoc201508026 shu

Investigation on the Mechanism for N-Methylindole and Keto Ester Catalyzed by InX₃ (X=F, Br)

1.
College of Chemistry and Material Science, Sichuan Normal University, Chengdu 610066

Corresponding author: Li Laicai,
Received Date: 26 August 2015
Available Online: 21 October 2015
Fund Project: 四川省教育厅自然科学基金(No. 13ZA0150) (No. 13ZA0150)四川省科技厅自然科学基金(No. 2014JY0099)资助项目. (No. 2014JY0099)

The reaction mechanism for N-methylindole and keto ester catalyzed by InX₃ (X=F, Br) was studied by the density functional theory (DFT). The geometries and the frequencies of reactants, intermediates, transition states, and products have been calculated at the B3LYP/6-31+G(d, p) level, dichloroethane (DCE) is used as a solvent and the LanL2DZ basis has been used for In atom. Transition states have been confirmed by the corresponding vibration analysis and intrinsic reaction coordinate (IRC). In addition, nature bond orbital (NBO) and atoms in molecules (AIM) theories have been used to analyze orbital interactions and bond natures. The results showed that the activation energies of rate-determining steps in which N-methylindole reacted with keto ester to form 1,2-adduct and 1,4-adduct were 25.62 and 12.52 kcal/mol catalyzed by InF₃ while those were 26.87 and 13.95 kcal/mol when the reaction was catalyzed by InBr₃under the same conditions. Comparing the results of our research, InF₃ can effectively catalyze the reaction, and the 1,4-adduct was more likely to be produced. The final result of our theory study agreed with the experimental data, meanwhile, self-consistent reaction field (SCRF) was carried out using the polarized continuum model (PCM) at the same theoretical level for geometry optimizations and frequency calculations in five different salvations. We predicted that the productivity to form 1,4-adduct was more higher catalyzed by InF₃ in the solvent of dimethyl sulfoxide (DMSO).
- density functional theory,
- N-methylindole,
- reaction mechanism,
- solvation
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沈阳化工大学材料科学与工程学院沈阳 110142

Investigation on the Mechanism for N-Methylindole and Keto Ester Catalyzed by InX3 (X=F, Br)

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通讯作者: 陈斌, bchen63@163.com

Investigation on the Mechanism for N-Methylindole and Keto Ester Catalyzed by InX₃ (X=F, Br)