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Regioselectivity in Sonogashira synthesis of 6-(4-nitrobenzyl)-2-phenylthiazolo[3,2-b]1,2,4-triazole: a quantum chemistry study

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Abstract

In the present research, the experimentally observed regioselectivity in Sonogashira synthesis of 6-(4-nitrobenzyl)-2-phenylthiazolo[3,2-b]1,2,4triazole has been modeled by means of density functional theory (DFT) employed to investigate the structural and thermochemical aspects of this synthesis in the gas and solution phases. Comparison of our calculated structural parameters of the title compound with the available X-ray crystallographical data demonstrate a reliable agreement. Then, the effect of two different solvents, DMF and ethanol, are examined via polarized continuum model calculations, showing a significant decrease in the computed values of the reaction enthalpy and free energy changes compared with the gas phase results. We have also considered two tautomeric structures of the intermediate species that it seems the mode of its intermolecular cyclization has an important role in regioselectivity of the final products. Moreover, all obtained results in the gas and solution phases also confirm that the synthesis of the title compound is thermodynamically more favorable than the other regioisomeric product. We also discuss the thermodynamical feasibility of this reaction at higher temperatures. Finally, we concentrate on the survey of substituent effect by choosing electron-withdrawing and electron-donating groups on the aryl iodide. Our calculated thermochemical data in the gas and solution phases indicate that the use of electron-withdrawing moieties is more favorable thermodynamically than electron-donating ones which has been previously concluded via the experimental elucidations.

A DFT study on regioselectivity

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Acknowledgments

The authors gratefully acknowledge the partial financial support received from the research council of Alzahra University. We have also thank to Prof. Mitra Ghassemzadeh for providing us X-ray crystallographical data. The first author is also grateful to Dr. M.H. Karimi-Jafari for his invaluable comments.

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Science, Alzahra University, Vanak, Tehran, Iran

    Tayebeh Hosseinnejad & Majid M. Heravi

  2. Chemistry & Chemical Engineering Research Center of Iran (CCERCI), P. O. Box 14335-186, Tehran, Iran

    Rohoullah Firouzi

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  1. Tayebeh Hosseinnejad
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  2. Majid M. Heravi
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  3. Rohoullah Firouzi
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Correspondence to Tayebeh Hosseinnejad.

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Hosseinnejad, T., Heravi, M.M. & Firouzi, R. Regioselectivity in Sonogashira synthesis of 6-(4-nitrobenzyl)-2-phenylthiazolo[3,2-b]1,2,4-triazole: a quantum chemistry study. J Mol Model 19, 951–961 (2013). https://doi.org/10.1007/s00894-012-1639-1

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  • DOI: https://doi.org/10.1007/s00894-012-1639-1

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