Insights into some Diels-Alder cycloadditions via the electrostatic potential and the reaction force constant

Jane S. Murray, Diana Yepes, Pablo Jaque, Peter Politzer

Resultado de la investigación: Article

12 Citas (Scopus)

Resumen

We have investigated computationally a series of 18 Diels-Alder cycloadditions, involving four dienes (butadiene, 2-hydroxybutadiene, cyclopentadiene and cyclohexadiene) and variously-substituted ethylenes and acetylenes as dienophiles. It is demonstrated that the respective molecular electrostatic potentials can be used to provide insight into the initial modes of interaction of the dienes and dienophiles, focusing particularly upon the synchronicities and nonsynchronicities of the processes. This is shown to complement predictions based upon the profiles of the reaction force constants κ(ξ) in the transition regions along the intrinsic reaction coordinates ξ: one κ(ξ) minimum ~ synchronicity, a minimum and a shoulder ~ moderate nonsynchronicity, two minima ~ strong nonsynchronicity. Temporal aspects of the reactions can also be examined through κ(ξ).

Idioma originalEnglish
Páginas (desde-hasta)270-280
Número de páginas11
PublicaciónComputational and Theoretical Chemistry
Volumen1053
DOI
EstadoPublished - 1 feb 2015

Huella dactilar

Ethylenes
Cyclopentanes
Alkynes
Cycloaddition
Cycloaddition Reaction
cycloaddition
Static Electricity
Electrostatics
dienes
electrostatics
butadiene
shoulders
acetylene
complement
ethylene
profiles
predictions
1,3-butadiene
1,4-cyclohexadiene
interactions

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Biochemistry
  • Condensed Matter Physics

Citar esto

Murray, Jane S. ; Yepes, Diana ; Jaque, Pablo ; Politzer, Peter. / Insights into some Diels-Alder cycloadditions via the electrostatic potential and the reaction force constant. En: Computational and Theoretical Chemistry. 2015 ; Vol. 1053. pp. 270-280.
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Insights into some Diels-Alder cycloadditions via the electrostatic potential and the reaction force constant. / Murray, Jane S.; Yepes, Diana; Jaque, Pablo; Politzer, Peter.

En: Computational and Theoretical Chemistry, Vol. 1053, 01.02.2015, p. 270-280.

Resultado de la investigación: Article

TY - JOUR

T1 - Insights into some Diels-Alder cycloadditions via the electrostatic potential and the reaction force constant

AU - Murray, Jane S.

AU - Yepes, Diana

AU - Jaque, Pablo

AU - Politzer, Peter

PY - 2015/2/1

Y1 - 2015/2/1

N2 - We have investigated computationally a series of 18 Diels-Alder cycloadditions, involving four dienes (butadiene, 2-hydroxybutadiene, cyclopentadiene and cyclohexadiene) and variously-substituted ethylenes and acetylenes as dienophiles. It is demonstrated that the respective molecular electrostatic potentials can be used to provide insight into the initial modes of interaction of the dienes and dienophiles, focusing particularly upon the synchronicities and nonsynchronicities of the processes. This is shown to complement predictions based upon the profiles of the reaction force constants κ(ξ) in the transition regions along the intrinsic reaction coordinates ξ: one κ(ξ) minimum ~ synchronicity, a minimum and a shoulder ~ moderate nonsynchronicity, two minima ~ strong nonsynchronicity. Temporal aspects of the reactions can also be examined through κ(ξ).

AB - We have investigated computationally a series of 18 Diels-Alder cycloadditions, involving four dienes (butadiene, 2-hydroxybutadiene, cyclopentadiene and cyclohexadiene) and variously-substituted ethylenes and acetylenes as dienophiles. It is demonstrated that the respective molecular electrostatic potentials can be used to provide insight into the initial modes of interaction of the dienes and dienophiles, focusing particularly upon the synchronicities and nonsynchronicities of the processes. This is shown to complement predictions based upon the profiles of the reaction force constants κ(ξ) in the transition regions along the intrinsic reaction coordinates ξ: one κ(ξ) minimum ~ synchronicity, a minimum and a shoulder ~ moderate nonsynchronicity, two minima ~ strong nonsynchronicity. Temporal aspects of the reactions can also be examined through κ(ξ).

KW - Diels-Alder cycloadditions

KW - Molecular electrostatic potentials

KW - Reaction force

KW - Reaction force constant

KW - Synchronicity/nonsynchronicity

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