6533b851fe1ef96bd12aa0cb

RESEARCH PRODUCT

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

Ponnadurai RamasamiHassan H. AbdallahLuis R. DomingoJohn A. JouleLydia RhymanSabina Jhaumeer-laulloo

subject

Organic ChemistryRegioselectivityBiochemistryMedicinal chemistryCycloadditionGas phasechemistry.chemical_compoundchemistryDrug Discovery13-Dipolar cycloadditionStructural isomerOrganic chemistryReactivity (chemistry)Density functional theoryMethyl acrylate

description

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 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.

yearjournalcountryeditionlanguage
2011-10-01Tetrahedron
https://doi.org/10.1016/j.tet.2011.08.021