A density functional study of the Claisen rearrangement of allyl aryl ether, allyl arylamine, allyl aryl thio ether, and a series of meta-substituted molecules through reactivity and selectivity profiles

Badhin Gómez, Pratim K. Chattaraj, E. Chamorro, R. Contreras, P. Fuentealba

Resultado de la investigación: Contribución a una revistaArtículorevisión exhaustiva

43 Citas (Scopus)

Resumen

The Claisen rearrangement of allyl phenyl ether, allyl phenylamine, and allyl phenyl thioether, together with the family of H, CH3, OCH3, Cl, F, and CN, meta-substituted molecules, is studied within a density functional framework with B3LYP exchange-correlation energy functionals and 6-311G** basis set. Reactants, intermediates, and products have equilibrium configurations (with no imaginary frequency), and the two transition states possess one imaginary frequency each corroborating the proposed mechanism of a [3,3]-sigmatropic rearrangement. The energy profile for the systems containing oxygen and nitrogen atoms mirrors the hardness profile along the reaction path in agreement with the maximum hardness principle. However, the molecules with sulfur atom do not follow the maximum hardness principle. This is explained in terms of the participation of the highest occupied molecular orbital (HOMO) in the reaction. The minimum polarizability principle is obeyed in all cases.

Idioma originalInglés
Páginas (desde-hasta)11227-11233
Número de páginas7
PublicaciónJournal of Physical Chemistry A
Volumen106
N.º46
DOI
EstadoPublicada - 21 nov 2002

Áreas temáticas de ASJC Scopus

  • Química física y teórica

Huella

Profundice en los temas de investigación de 'A density functional study of the Claisen rearrangement of allyl aryl ether, allyl arylamine, allyl aryl thio ether, and a series of meta-substituted molecules through reactivity and selectivity profiles'. En conjunto forman una huella única.

Citar esto