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A theoretical investigation on the mechanism of cycloaddition reactions of fulvenes with tetrazine and diazacyclopentadienone derivatives

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Abstract

The mechanism of cycloaddition reactions for 6-dimethylaminofulvene and 6,6-diphenylfulvene with tetrazine and diazacyclopentadienone are studied by DFT at the MPWB1K/cc-pVDZ level of theory. The energy results indicated that the [6 + 4] cycloaddition reaction of 6-dimethylaminofulvene with tetrazine and diazacyclopentadienone derivatives proceeds in a stepwise fashion, while the [2 + 4] cycloaddition reaction of 6,6-diphenylfulvene might proceed in a one-step fashion. Our calculations showed some unfavorable processes with unstable cycloadducts arising from [4 + 2] cycloaddition reactions which are unobserved in the experimental results. Also, an analysis of the Parr functions for the reactants allows us to provide an explanation of the selectivity of these cycloaddition reactions.

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Acknowledgements

The authors wish to acknowledge Dr. Louise S. Price, University College London, UK, for reading the manuscript and providing valuable suggestions.

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  1. Department of Chemistry, Islamic Azad University, P.O. box 755, Babol branch, Babol, Iran

    Mina Haghdadi, Mina Alashti & Hassan Ghasemnejad Bosra

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  1. Mina Haghdadi
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Correspondence to Mina Haghdadi.

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Haghdadi, M., Alashti, M. & Bosra, H.G. A theoretical investigation on the mechanism of cycloaddition reactions of fulvenes with tetrazine and diazacyclopentadienone derivatives. Struct Chem 29, 1511–1523 (2018). https://doi.org/10.1007/s11224-018-1138-9

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