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DFT study on the gold(I)-catalyzed cycloaddition and rearrangement reactions of allene-containing allylic silyl ether

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Abstract

The DFT calculation at the B3LYP/B3LYP-D3(BJ) level was carried out to explore the reaction mechanism of the synthesis of spirocyclo[4,5]decane skeleton by gold-catalyzed allenyl compounds. The more accurate energy under the CH3CN solvent in the experiment is calculated by the single-point energy of the SMD model. Computational studies have shown that the reaction consists of three main steps: intramolecular cycloaddition of the end group carbon atoms of allenyl and vinyl groups, the semipinacol rearrangement process in which the four-membered ring is reconstructed into the five-membered ring, the elimination reaction releases the catalyst and obtains the product. The calculation results show that Zheng et al. reported that the gold-catalyzed synthesis reaction can easily occur under the experimental conditions due to its low activation free energy (12.07–15.49 kcal/mol). Furthermore, it was found that the MOMO(CH2)2 substituent has higher reactivity than the corresponding reactant of the phenyl substituent.

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Acknowledgements

We are grateful to the reviewers for their invaluable suggestions.

Funding

This work was supported by the Special Research PLan of Shaanxi Provincial Department of Education, China (No. 18JK0340).

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Authors and Affiliations

  1. School of Environmental and Chemical Engineering, Xi’an Polytechnic University, Xi’an, 710048, Shaanxi, China

    YaMei Zhao, MengDan Huo & HongJi Zhou

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  1. YaMei Zhao
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Contributions

YaMei Zhao: problem selection, writing, and data analysis.

MengDan Huo: methods, project management, result analysis, manuscript editing.

HongJi Zhou: data analysis, writing.

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Correspondence to YaMei Zhao.

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Zhao, Y., Huo, M. & Zhou, H. DFT study on the gold(I)-catalyzed cycloaddition and rearrangement reactions of allene-containing allylic silyl ether. J Mol Model 28, 25 (2022). https://doi.org/10.1007/s00894-021-05004-8

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