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: Article

34 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 originalEnglish
Páginas (desde-hasta)348-356
Número de páginas9
PublicaciónJournal of Organic Chemistry
Volumen72
N.º2
DOI
EstadoPublished - 19 ene 2007

Huella dactilar

Regioselectivity
Density functional theory
Carbon
Cyclization
Molecules
Charge transfer
Nitrogen
Electrons

ASJC Scopus subject areas

  • Organic Chemistry

Citar esto

Pintér, B. ; De Proft, F. ; Van Speybroeck, V. ; Hemelsoet, K. ; Waroquier, M. ; Chamorro, E. ; Veszprémi, T. ; Geerlings, P. / Spin-polarized conceptual density functional theory study of the regioselectivity in ring closures of radicals. En: Journal of Organic Chemistry. 2007 ; Vol. 72, N.º 2. pp. 348-356.
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abstract = "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).",
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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, vol. 72, n.º 2, pp. 348-356. https://doi.org/10.1021/jo0613885

Spin-polarized conceptual density functional theory study of the regioselectivity in ring closures of radicals. / Pintér, B.; De Proft, F.; Van Speybroeck, V.; Hemelsoet, K.; Waroquier, M.; Chamorro, E.; Veszprémi, T.; Geerlings, P.

En: Journal of Organic Chemistry, Vol. 72, N.º 2, 19.01.2007, p. 348-356.

Resultado de la investigación: Article

TY - JOUR

T1 - Spin-polarized conceptual density functional theory study of the regioselectivity in ring closures of radicals

AU - Pintér, B.

AU - De Proft, F.

AU - Van Speybroeck, V.

AU - Hemelsoet, K.

AU - Waroquier, M.

AU - Chamorro, E.

AU - Veszprémi, T.

AU - Geerlings, P.

PY - 2007/1/19

Y1 - 2007/1/19

N2 - 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).

AB - 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).

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