Exclusive solvent-controlled regioselective catalytic synthesis of potentially bioactive imidazolidineiminodithiones: NMR analysis, computational studies and X-ray crystal structures
Herein, we describe the first consistent regiospecific reaction of isothiocyanates with a variety of substituted N-arylcyanothioformamides in a 1:1 molar ratio to generate a series of imidazolidineiminodithiones decorated with a multitude of functional groups on both aromatic rings. The reaction is...
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sg-ntu-dr.10356-1815892024-12-10T04:53:41Z Exclusive solvent-controlled regioselective catalytic synthesis of potentially bioactive imidazolidineiminodithiones: NMR analysis, computational studies and X-ray crystal structures Moussa, Ziad Saada, Sara Paz, Alejandro Perez Alzamly, Ahmed Judeh, Zaher M. A. Alshehhi, Aaesha R. Khudhair, Aisha Almheiri, Salama A. Al-Masri, Harbi Tomah Ahmed, Saleh A. School of Chemical and Biomedical Engineering Engineering Isothiocyanates Imidazolidineiminodithiones Herein, we describe the first consistent regiospecific reaction of isothiocyanates with a variety of substituted N-arylcyanothioformamides in a 1:1 molar ratio to generate a series of imidazolidineiminodithiones decorated with a multitude of functional groups on both aromatic rings. The reaction is carried out at room temperature using a 20 mol% catalytic amount of triethylamine with DMF as the solvent to selectively form the mentioned products with exclusive regioselectivity. The methodology features wide substrate scope, no requirement for chromatography, and good to high reaction yields. The products were isolated by simple ether/brine extraction and the structures were verified by multinuclear NMR spectroscopy and high accuracy mass measurements. The first conclusive molecular structure elucidation of the observed regioisomer was established by single-crystal X-ray diffraction analysis. Likewise, the tautomer of the N-arylcyanothioformamide reactant was proven by X-ray diffraction analysis. Density functional theory computations at the B3LYP-D4/def2-TZVP level in implicit DMF solvent were conducted to support the noted regiochemical outcome and proposed mechanism. Published version Ziad Moussa is grateful to the United Arab Emirates University (UAEU) and to the Research Office for supporting the research developed in his laboratory and reported herein (SUREPLUS Grant code G00004305, UPAR Grant code G00004605). 2024-12-10T04:53:40Z 2024-12-10T04:53:40Z 2024 Journal Article Moussa, Z., Saada, S., Paz, A. P., Alzamly, A., Judeh, Z. M. A., Alshehhi, A. R., Khudhair, A., Almheiri, S. A., Al-Masri, H. T. & Ahmed, S. A. (2024). Exclusive solvent-controlled regioselective catalytic synthesis of potentially bioactive imidazolidineiminodithiones: NMR analysis, computational studies and X-ray crystal structures. Molecules, 29(16), 3958-. https://dx.doi.org/10.3390/molecules29163958 1420-3049 https://hdl.handle.net/10356/181589 10.3390/molecules29163958 39203036 2-s2.0-85202646868 16 29 3958 en Molecules © 2024 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ 4.0/). application/pdf |
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Engineering Isothiocyanates Imidazolidineiminodithiones |
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Engineering Isothiocyanates Imidazolidineiminodithiones Moussa, Ziad Saada, Sara Paz, Alejandro Perez Alzamly, Ahmed Judeh, Zaher M. A. Alshehhi, Aaesha R. Khudhair, Aisha Almheiri, Salama A. Al-Masri, Harbi Tomah Ahmed, Saleh A. Exclusive solvent-controlled regioselective catalytic synthesis of potentially bioactive imidazolidineiminodithiones: NMR analysis, computational studies and X-ray crystal structures |
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Herein, we describe the first consistent regiospecific reaction of isothiocyanates with a variety of substituted N-arylcyanothioformamides in a 1:1 molar ratio to generate a series of imidazolidineiminodithiones decorated with a multitude of functional groups on both aromatic rings. The reaction is carried out at room temperature using a 20 mol% catalytic amount of triethylamine with DMF as the solvent to selectively form the mentioned products with exclusive regioselectivity. The methodology features wide substrate scope, no requirement for chromatography, and good to high reaction yields. The products were isolated by simple ether/brine extraction and the structures were verified by multinuclear NMR spectroscopy and high accuracy mass measurements. The first conclusive molecular structure elucidation of the observed regioisomer was established by single-crystal X-ray diffraction analysis. Likewise, the tautomer of the N-arylcyanothioformamide reactant was proven by X-ray diffraction analysis. Density functional theory computations at the B3LYP-D4/def2-TZVP level in implicit DMF solvent were conducted to support the noted regiochemical outcome and proposed mechanism. |
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School of Chemical and Biomedical Engineering |
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School of Chemical and Biomedical Engineering Moussa, Ziad Saada, Sara Paz, Alejandro Perez Alzamly, Ahmed Judeh, Zaher M. A. Alshehhi, Aaesha R. Khudhair, Aisha Almheiri, Salama A. Al-Masri, Harbi Tomah Ahmed, Saleh A. |
format |
Article |
author |
Moussa, Ziad Saada, Sara Paz, Alejandro Perez Alzamly, Ahmed Judeh, Zaher M. A. Alshehhi, Aaesha R. Khudhair, Aisha Almheiri, Salama A. Al-Masri, Harbi Tomah Ahmed, Saleh A. |
author_sort |
Moussa, Ziad |
title |
Exclusive solvent-controlled regioselective catalytic synthesis of potentially bioactive imidazolidineiminodithiones: NMR analysis, computational studies and X-ray crystal structures |
title_short |
Exclusive solvent-controlled regioselective catalytic synthesis of potentially bioactive imidazolidineiminodithiones: NMR analysis, computational studies and X-ray crystal structures |
title_full |
Exclusive solvent-controlled regioselective catalytic synthesis of potentially bioactive imidazolidineiminodithiones: NMR analysis, computational studies and X-ray crystal structures |
title_fullStr |
Exclusive solvent-controlled regioselective catalytic synthesis of potentially bioactive imidazolidineiminodithiones: NMR analysis, computational studies and X-ray crystal structures |
title_full_unstemmed |
Exclusive solvent-controlled regioselective catalytic synthesis of potentially bioactive imidazolidineiminodithiones: NMR analysis, computational studies and X-ray crystal structures |
title_sort |
exclusive solvent-controlled regioselective catalytic synthesis of potentially bioactive imidazolidineiminodithiones: nmr analysis, computational studies and x-ray crystal structures |
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2024 |
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https://hdl.handle.net/10356/181589 |
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1819112950261088256 |