The Mysticism of Pericyclic Reactions: A Contemporary Rationalisation of Organic Reactivity Based on Electron Density Analysis

Luis R. Domingo, Mar Ríos-Gutiérrez, Bernard Silvi, Patricia Pérez

Resultado de la investigación: Contribución a una revistaArtículorevisión exhaustiva

31 Citas (Scopus)

Resumen

The molecular mechanism of the five most representative “pericyclic reactions” has been studied by applying molecular electron density theory (MEDT). The different phases into which the reaction paths are topologically divided can be regrouped into four well-characterised steps: 1) the rupture of the C–C double bonds, 2) the formation of pseudoradical centres at the interacting carbons, 3) the formation of new C–C single bonds and 4) the formation of new C–C double bonds in the final products. Consequently, the bonding changes in these reactions are neither concerted nor cyclic. As the transition-state structures are located at the end of the large first group of phases or in the narrow second group, the high activation enthalpies found in these reactions are mainly associated with the rupture of C–C double bonds. The present MEDT study makes it possible to rule out the definition of “pericyclic reactions”, made by Woodward and Hoffmann in 1969, in which “all first order changes in bonding relationships take place in concert on a closed curve”.

Idioma originalInglés
Páginas (desde-hasta)1107-1120
Número de páginas14
PublicaciónEuropean Journal of Organic Chemistry
Volumen2018
N.º9
DOI
EstadoPublicada - 7 mar 2018

Áreas temáticas de ASJC Scopus

  • Química física y teórica
  • Química orgánica

Huella

Profundice en los temas de investigación de 'The Mysticism of Pericyclic Reactions: A Contemporary Rationalisation of Organic Reactivity Based on Electron Density Analysis'. En conjunto forman una huella única.

Citar esto