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The mechanisms for N-heterocyclic olefin-catalyzed formation of cyclic carbonate from CO2 and propargylic alcohols

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Abstract

The mechanistic details of N-heterocyclic olefin-catalyzed formation of cyclic carbonate from CO2 and propargylic alcohols were investigated by DFT calculations. Six mechanisms, four for the formation of five-membered cyclic carbonate (M-A, M-B, M-B’ and M-C), and two for six-membered cyclic carbonate (M-D and M-E), were fully investigated. The energy profiles in dichloromethane showed that M-B is the predominant reaction with the lowest barrier of 31.99 kcal mol−1, while M-C and M-D may be kinetically competitive to M-B. The very high activation energy of 45.37 kcal mol-1, 57.07 kcal mol-1 and 59.61 kcal mol−1 for M-A, M-B’ and M-E, respectively, suggest that they are of lesser importance in the overall mechanism.

Formations of five-membered ring product and six-membered ring product are kinetically competitive, but five-membered ring product is thermodynamically more preferable.

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Notes

  1. Note that intermediate 9 may take place via another reaction in which the H atom on the O1 atom migrates to the C3 atom, and the whole molecule decomposes to allyene, acetone and CO2. The barrier height for this reaction is 51.27 kcal mol−1 (relative to initial reactants)

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Acknowledgments

This project is supported by the Scientific Research Foundation for the Returned Overseas Chinese Scholars, Shanxi Province, P. R. China. Project No. 2008–75.

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Authors and Affiliations

  1. School of Chemistry and Materials Science, Shanxi Normal University, Linfen, 041004, China

    Zhi-E Yan, Li-hui Guo & Xiang Zhang

  2. Department of Chemistry, Taiyuan Normal University, Taiyuan, 030031, China

    Rui-Ping Huo

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  1. Zhi-E Yan
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Correspondence to Xiang Zhang.

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Yan, ZE., Huo, RP., Guo, Lh. et al. The mechanisms for N-heterocyclic olefin-catalyzed formation of cyclic carbonate from CO2 and propargylic alcohols. J Mol Model 22, 94 (2016). https://doi.org/10.1007/s00894-016-2959-3

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  • DOI: https://doi.org/10.1007/s00894-016-2959-3

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