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DFT study on the mechanism of InBr3-catalyzed [2+2] cycloaddition of allyltrimethylsilane with alkynones

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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 InBr3 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 InBr3-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 InX3(X = Cl, Br, I) catalyst for this cycloaddition. This is a good explanation for the experimental data that InBr3 and InI3 would be the most effective catalysts.

M06-2X calculation was done to study the reaction mechanism for the [2+2] cycloaddition of allyltrimethylsilane with alkynones by InBr3 catalyst. The reaction involves attack of the unsaturated carbon atoms of the alkynone by π electrons and a closed-loop process. The cyclobutenone product of silicon in the 2-position of the ketone group is more favored.

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Acknowledgements

This work was supported by Longyuan young creative talents to support projects, Gansu Province (2014-98), and the Natural Science Foundation of Department of Education, Gansu Province (2016B-121). We are grateful to the Gansu Province Supercomputer Center for essential support. We are grateful to the Reviewers for their invaluable suggestions.

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  1. College of Chemical Engineering, Lanzhou University of Arts and Science, Lanzhou, 730010, China

    XING HUI ZHANG

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Tables giving Cartesian coordinates for the calculated stationary structures obtained from the DFT calculations are given in Supplementary Information, which is available at www.ias.ac.in/chemsci.

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ZHANG, X.H. DFT study on the mechanism of InBr3-catalyzed [2+2] cycloaddition of allyltrimethylsilane with alkynones. J Chem Sci 129, 505–513 (2017). https://doi.org/10.1007/s12039-017-1260-z

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