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The mechanism of electrophilic addition of singlet oxygen to pyrrolic ring

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Abstract

Pyrrolic compounds assume an important role in the chemistry of living organisms, coal surrogates and novel drugs. However, literature reports a few studies on their reactivity towards prominent oxidising agents. This contribution presents a comprehensive mechanistic study of the oxidation of unsubstituted pyrrole with singlet oxygen (O2 1∆g) by deploying a quantum chemical framework leading to the production of succinimide, as the major products, through a Diels–Alder addition of O2 1∆g to the aromatic ring. Other products such as maleimide, hydroperoxide, formamide and epoxide adducts appear to form via insignificant channels. The primary Diels–Alder channel encompasses a barrier of 41 kJ/mol with a fitted rate constant of k(T) = 1.87 × 10−13 exp(− 48,000/RT) cm3 mol−1 s−1. Furthermore, a kinetic study has been undertaken to investigate the influence of substituents on reaction rate of the Diels–Alder addition of singlet oxygen to a pyrrolic ring. The results clarify that electropositive substituents such as BeH and BH2 operate as π-acceptors and thus deactivate the ring towards electrophilic attack of singlet oxygen. However, substituents comprising of strong π-donors, e.g., NH2 and OH, destabilise the ring structure, increasing its oxidation reactivity.

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Acknowledgements

This study has been supported by grants of computing time from the National Computational Infrastructure (NCI) and from the Pawsey Supercomputing Centre, Australia, as well as funds from the Australian Research Council (ARC). N.Z. thanks Murdoch University for the award of postgraduate scholarships. Authors thank Dr Mansour Almatarneh (The University of Jordan) for fruitful discussion during the revision of the manuscript.

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Authors and Affiliations

  1. Discipline of Chemistry and Physics, College of Science, Health, Engineering and Education, Murdoch University, 90 South Street, Murdoch, WA, 6150, Australia

    Nassim Zeinali, Ibukun Oluwoye, Mohammednoor Altarawneh & Bogdan Z. Dlugogorski

  2. Department of Chemical Engineering, Al-Hussein Bin Talal University, Ma’an, Jordan

    Mohammednoor Altarawneh

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  1. Nassim Zeinali
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  2. Ibukun Oluwoye
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  3. Mohammednoor Altarawneh
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  4. Bogdan Z. Dlugogorski
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Correspondence to Mohammednoor Altarawneh.

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Zeinali, N., Oluwoye, I., Altarawneh, M. et al. The mechanism of electrophilic addition of singlet oxygen to pyrrolic ring. Theor Chem Acc 138, 90 (2019). https://doi.org/10.1007/s00214-019-2478-2

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