Spin-polarized conceptual density functional theory study of the regioselectivity in ring closures of radicals

B. Pintér, F. De Proft, V. Van Speybroeck, K. Hemelsoet, M. Waroquier, E. Chamorro, T. Veszprémi, P. Geerlings

Resultado de la investigación: Contribución a una revistaArtículo

35 Citas (Scopus)

Resumen

The regioselectivity of ring-forming radical reactions is investigated within the framework of the so-called spin-polarized conceptual density functional theory. Two different types of cyclizations were studied. First, a series of model reactions of alkyl- and acyl-substituted radicals were investigated. Next, attention was focused on the radical cascade cyclizations of N-alkenyl-2-aziridinylmethyl radicals (a three-step mechanism). In both of these reactions, the approaching radical (carbon or nitrogen centered) adds to a carbon-carbon double bond within the same molecule to form a radical ring compound. In this process, the number of electrons is changing from a local point of view (a charge transfer occurs from one part of the molecule to another one) at constant global spin number Ns (both the reactant and the product ring compound are in the doublet state). It is shown that the experimentally observed regioselectivities for these ring-closure steps can be predicted using the spin-polarized Fukui functions for radical attack, f NNO(r).

Idioma originalInglés
Páginas (desde-hasta)348-356
Número de páginas9
PublicaciónJournal of Organic Chemistry
Volumen72
N.º2
DOI
EstadoPublicada - 19 ene 2007

Áreas temáticas de ASJC Scopus

  • Química orgánica

Huella Profundice en los temas de investigación de 'Spin-polarized conceptual density functional theory study of the regioselectivity in ring closures of radicals'. En conjunto forman una huella única.

  • Citar esto

    Pintér, B., De Proft, F., Van Speybroeck, V., Hemelsoet, K., Waroquier, M., Chamorro, E., Veszprémi, T., & Geerlings, P. (2007). Spin-polarized conceptual density functional theory study of the regioselectivity in ring closures of radicals. Journal of Organic Chemistry, 72(2), 348-356. https://doi.org/10.1021/jo0613885