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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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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DOI: https://doi.org/10.1007/s10562-023-04374-3