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DFT Studies on Mechanism of Organocatalytic Metal-Free Click 32CA Reaction for Synthesis of NH-1,2,3-triazoles

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Abstract

The mechanism of enamine-mediated organocatalytic [3 + 2] cycloaddition (32CA) reaction of Hagemann’s ester to p-toluenesulfonyl azide in the present L-proline as a catalyst has been investigated using M06-2X functional with the 6-31+G(d) basis set. The effects of the different solvents were studied with a 6-311+G(d,p) basis set. In addition, the effects of the keto ester substitutions: one model system M1 (R1 = CH3 and R2 = H) and two real systems R2 (R1 = R2 = Me) and R3 (R1 = Et and R2 = Me) also studied in this work. DFT results indicated that the different solvents show the same effect, which leads to a decrease in the ΔG298 along the reaction pathway compared to the gas phase. Moreover, the model system M1 has a lower activation free energy (17.5 kcal/mol) than real systems R2 and R3 by about 3.8 and 3.2 kcal/mol in the solution phase (DMSO), respectively. Analysis of the global and local reactivity indices of the reactants was performed in the gas and solution phases.

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Science, Tishreen University, Lattakia, Syrian Arab Republic

    Mohammad Abd Al-Hakim Badawi

  2. Department of Chemistry, King Saud University, P.O.Box 11495, Riyadh, Kingdom of Saudi Arabia

    Maha I. Al-Zaben

  3. Department of Chemistry, St Berchmans College (Autonomous), Mahatma Gandhi University, Changanassery, Kerala, 686101, India

    Renjith Thomas

  4. Centre for Theoretical and Computational Chemistry, St Berchmans College (Autonomous), Changanassery, Kerala, 686101, India

    Renjith Thomas

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Al-Hakim Badawi, M.A., Al-Zaben, M.I. & Thomas, R. DFT Studies on Mechanism of Organocatalytic Metal-Free Click 32CA Reaction for Synthesis of NH-1,2,3-triazoles. Catal Lett 154, 1134–1141 (2024). https://doi.org/10.1007/s10562-023-04374-3

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