0000000000505763
AUTHOR
Sabina Jhaumeer-laulloo
showing 2 related works from this author
The 1,3-dipolar cycloaddition of 1H-pyridinium-3-olate and 1-methylpyridinium-3-olate with methyl acrylate: a density functional theory study
2010
The 1,3-dipolar cycloaddition reaction of 1-substituted pyridinium 3-olates with methyl acrylate is studied using density functional theory (DFT) method at the B3LYP/6-31G(d) level. The molecular mechanisms of the possible stereo- and regio-chemical pathways are characterized and explored. Solvent effects are also evaluated by the polarizable continuum model (PCM). Analysis of the results shows that there are relevant differences in the reaction pathways between the gas phase and with solvent. Only results in solvent phase are in accord with literature experimental results where 6-substituted 8-azabicyclo[3.2.1]oct-3-en-2-ones are formed preferentially. These polar cycloaddition reactions t…
1,3-Dipolar cycloaddition of 1H-pyrazinium-3-olate and N1- and C-methyl substituted pyrazinium-3-olates with methyl acrylate: a density functional th…
2011
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-diazabicyclo[3.2.1]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 cycloadd…