A DFT Study of Inter- and Intramolecular Aryne Ene Reactions

Patricia Pérez, Luis R. Domingo

Resultado de la investigación: Article

20 Citas (Scopus)

Resumen

The molecular mechanisms of inter- and intramolecular aryne-ene reactions have been theoretically studied by DFT methods at the MPWB1K/6-311G(d,p) level. These reactions proceed through a one-step mechanism via nearly asynchronous transition states (TSs), in which the C-C single bond formation is slightly more advanced than the hydrogen transfer process. These ene reactions show very low activation enthalpies (<1 kcal/mol) and are strongly exothermic by more than 73 kcal/mol. An electron localisation function (ELF) topological analysis of the changes of electron density during these ene reactions indicates that the bonding changes are nonconcerted. ELF topological analysis of the electron density in the C1-C2 bonding region of benzyne indicates that the 1,2-pseudodiradical vinyl structure, rather than a structure with a C=C triple bond, is responsible for the very high reactivity of these species.

Idioma originalEnglish
Páginas (desde-hasta)2826-2834
Número de páginas9
PublicaciónEuropean Journal of Organic Chemistry
Volumen2015
N.º13
DOI
EstadoPublished - 1 may 2015

Huella dactilar

Discrete Fourier transforms
Carrier concentration
Electrons
Hydrogen
Enthalpy
Chemical activation
electrons
reactivity
enthalpy
activation
hydrogen
single bond
benzyne

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry

Citar esto

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A DFT Study of Inter- and Intramolecular Aryne Ene Reactions. / Pérez, Patricia; Domingo, Luis R.

En: European Journal of Organic Chemistry, Vol. 2015, N.º 13, 01.05.2015, p. 2826-2834.

Resultado de la investigación: Article

TY - JOUR

T1 - A DFT Study of Inter- and Intramolecular Aryne Ene Reactions

AU - Pérez, Patricia

AU - Domingo, Luis R.

PY - 2015/5/1

Y1 - 2015/5/1

N2 - The molecular mechanisms of inter- and intramolecular aryne-ene reactions have been theoretically studied by DFT methods at the MPWB1K/6-311G(d,p) level. These reactions proceed through a one-step mechanism via nearly asynchronous transition states (TSs), in which the C-C single bond formation is slightly more advanced than the hydrogen transfer process. These ene reactions show very low activation enthalpies (<1 kcal/mol) and are strongly exothermic by more than 73 kcal/mol. An electron localisation function (ELF) topological analysis of the changes of electron density during these ene reactions indicates that the bonding changes are nonconcerted. ELF topological analysis of the electron density in the C1-C2 bonding region of benzyne indicates that the 1,2-pseudodiradical vinyl structure, rather than a structure with a C=C triple bond, is responsible for the very high reactivity of these species.

AB - The molecular mechanisms of inter- and intramolecular aryne-ene reactions have been theoretically studied by DFT methods at the MPWB1K/6-311G(d,p) level. These reactions proceed through a one-step mechanism via nearly asynchronous transition states (TSs), in which the C-C single bond formation is slightly more advanced than the hydrogen transfer process. These ene reactions show very low activation enthalpies (<1 kcal/mol) and are strongly exothermic by more than 73 kcal/mol. An electron localisation function (ELF) topological analysis of the changes of electron density during these ene reactions indicates that the bonding changes are nonconcerted. ELF topological analysis of the electron density in the C1-C2 bonding region of benzyne indicates that the 1,2-pseudodiradical vinyl structure, rather than a structure with a C=C triple bond, is responsible for the very high reactivity of these species.

KW - Arynes

KW - Density functional theory

KW - Ene reaction

KW - Reaction mechanisms

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DO - 10.1002/ejoc.201500139

M3 - Article

AN - SCOPUS:84928242175

VL - 2015

SP - 2826

EP - 2834

JO - Annalen der Pharmacie

JF - Annalen der Pharmacie

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