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- Title
DFT study on the mechanism of InBr-catalyzed [2+2] cycloaddition of allyltrimethylsilane with alkynones.
- Authors
ZHANG, XING
- Abstract
Density functional theory calculations at the M06-2X level were done to study the reaction mechanism and regioselectivity for the [2+2] cycloaddition of allyltrimethylsilane with alkynones using InBr as the catalyst. The solvent effect was described by the single-point calculations with SMD model in 1,2-dichloroethane. The calculation results prove that the InBr-catalyzed cycloaddition of allyltrimethylsilane to alkynones takes place through two possible pathways and get selective cyclobutenone products. The reaction involves two main steps: attack of unsaturated carbon atoms of the alkynone by the π electrons of allyltrimethylsilane and a closed-loop process. The process of forming cyclobutenone product of silicon in the 2-position of the ketone group is more favored and the barrier is 15.5 kcal/mol, while the energies for the cyclobutenone of 3-position product are relatively high of 21.2 kcal/mol. In addition, we calculated the catalytic activity of the InX(X = Cl, Br, I) catalyst for this cycloaddition. This is a good explanation for the experimental data that InBr and InI would be the most effective catalysts.
- Subjects
DENSITY functional theory; INDIUM bromides; RING formation (Chemistry); METHYLSILANE; CYCLOBUTENONES
- Publication
Journal of Chemical Sciences, 2017, Vol 129, Issue 4, p505
- ISSN
0974-3626
- Publication type
Article
- DOI
10.1007/s12039-017-1260-z