1,3-Dipolar cycloaddition of 1H-pyrazinium-3-olate and N1- and C-methyl substituted pyrazinium-3-olates with methyl acrylate: a density functional theory study |
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Authors: | Lydia RhymanHassan H Abdallah Sabina Jhaumeer-LaullooLuis R Domingo John A JoulePonnadurai Ramasami |
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Institution: | a Department of Chemistry, University of Mauritius, Réduit, Mauritius b School of Chemical Sciences, Universiti Sains Malaysia, 11800 Penang, Malaysia c Departamento de Química Orgánica, Universidad de Valencia, Dr. Moliner 50, 46100 Burjassot, Valencia, Spain d The School of Chemistry, The University of Manchester, Manchester M13 9PL, UK |
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Abstract: | A DFT study of the 1,3-dipolar cycloaddition of methyl acrylate to 1H-pyrazinium-3-olate and N1- and C-methyl substituted pyrazinium-3-olates, in the gas phase and in THF, has been carried out at the B3LYP/6-31G(d) level. Two stereoisomeric pathways, endo and exo, and two regioisomeric channels, 2-oxo-3,8-diazabicyclo3.2.1]octane-6-ester and 7-ester products, have been considered. Thermodynamic and kinetic parameters calculated at room temperature have been analyzed. The regioselectivity has been interpreted using reactivity indices. It is generally found that the exo pathway is preferred and the formation of the 6-esters is dominant. The theoretical data obtained for the cycloaddition reaction of 1,5-dimethylpyrazinium-3-olate with methyl acrylate are consistent with the literature where the 6-exo regioisomer is formed as the major cycloadduct. |
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