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Ascorbic acid as a multifunctional hydrogen bonding catalyst for Paal–Knorr synthesis of N-substituted mono- and bis-pyrroles: experimental and theoretical aspects

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Abstract

Ascorbic acid could be applied as a recyclable organocatalyst for the preparation of pyrroles via Paal–Knorr condensation of hexane-2,5-dione with various mono- and diamines. The reaction proceeded smoothly to afford the desired products in moderate to excellent yields under solvent-free conditions. Moreover, the investigations on diamine reactants revealed that both the amount of loaded catalyst and steric or electronic property of substrates are major factors in the selective formation of the corresponding bis-pyrrole or mono-pyrrole products. Density functional theory methods have been employed to provide a better understanding of the catalytic mechanism of ascorbic acid in this reaction. The optimized calculations pointed out the presence of three possible bifunctional hydrogen bond donor sites and one hydrogen bond acceptor site in the molecular structure of ascorbic acid. Although all four possible complexes were studied, the two bidentate hydrogen bond complexes between ascorbic acid and the carbonyl group of hexane-2,5-dione (average hydrogen bond distance ~ 1.8–1.9 Å) were the most stable complexes. MEP maps and NBO analysis of the complexes are in consistent with the obtained free energy. Furthermore, the reduced HOMO–LUMO energy gap values support an increase in the chemical reactivity of catalyzed hexane-2,5-dione toward aniline.

Graphical Abstract

Ascorbic acid could be applied as a recyclable bifunctional hydrogen bond organocatalyst for the preparation of pyrroles via Paal–Knorr condensation of hexane-2,5-dione with various mono- and diamines. The DFT calculations support the existence of bidentate hydrogen bond interactions of ascorbic acid with substrates which facilitates the reaction.

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Authors and Affiliations

  1. Applied Chemicals Synthesis Laboratory, Chemistry and Chemical Engineering Research Center of Iran, Pajoohesh Blvd., Km 17, Karaj Hwy, Tehran, 14968-13151, Iran

    Amin Ghaemi, Hossein Reza Darabi, Kioumars Aghapoor, Farshid Mohsenzadeh, Hani Sayahi, Maryam Farajpour Mojdehi, Yadollah Balavar & Hossein Farhangian

  2. UNIQUE Co. Ltd., 3-1976, Oono Town, Ichikawa, Chiba, 272-0805, Japan

    Hossein Taherzadeh

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  1. Amin Ghaemi
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Contributions

AG: Investigation, formal analysis. HRD: Project administration, conceptualization, writing—original draft, writing—review & editing. KA: Methodology, investigation, formal analysis, writing—review & editing. FM: Conceptualization, methodology, writing—review & editing. HS: Investigation, writing—review & editing. HT: Formal analysis. MFM: Software, theoretical calculations. YB: Investigation. HF: Software, theoretical calculations, editing. All authors read and approved the final manuscript. All authors reviewed the manuscript.

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Correspondence to Hossein Reza Darabi.

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Ghaemi, A., Darabi, H.R., Aghapoor, K. et al. Ascorbic acid as a multifunctional hydrogen bonding catalyst for Paal–Knorr synthesis of N-substituted mono- and bis-pyrroles: experimental and theoretical aspects. Res Chem Intermed 49, 4087–4102 (2023). https://doi.org/10.1007/s11164-023-05072-w

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