Understanding the origin of the asynchronicity in bond-formation in polar cycloaddition reactions. A DFT study of the 1,3-dipolar cycloaddition reaction of carbonyl ylides with 1,2-benzoquinones

L. R. Domingo, M. J. Aurell, P. Pérez, J. A. Sáez

Resultado de la investigación: Article

35 Citas (Scopus)

Resumen

The origin of the asynchronicity in bond-formation in polar cycloadditions has been studied by an ELF analysis of the electron reorganisation along the 1,3-dipolar cycloaddition of Padwa's carbonyl ylide 4 with the 1,2-benzoquinone 8. This reaction presents an unexpected asynchronous bond-formation, which is initialised through the nucleophilic attack of Padwa's carbonyl ylide on the carbonyl oxygen atom of the strongly electrophilically activated 1,2-benzoquinone. The present study allows for the establishment that along an asynchronous bond-formation, the more favourable two-center interaction begins at the most electrophilic center, which is the center with the highest spin density achieved through the charge transfer process, and not, as expected, at the center that presents the larger positive charge.

Idioma originalEnglish
Páginas (desde-hasta)1334-1342
Número de páginas9
PublicaciónRSC Advances
Volumen2
N.º4
DOI
EstadoPublished - 21 feb 2012

Huella dactilar

Benzoquinones
Cycloaddition
Discrete Fourier transforms
Charge transfer
Oxygen
Atoms
Electrons
2-benzoquinone

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

Citar esto

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AU - Domingo, L. R.

AU - Aurell, M. J.

AU - Pérez, P.

AU - Sáez, J. A.

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AB - The origin of the asynchronicity in bond-formation in polar cycloadditions has been studied by an ELF analysis of the electron reorganisation along the 1,3-dipolar cycloaddition of Padwa's carbonyl ylide 4 with the 1,2-benzoquinone 8. This reaction presents an unexpected asynchronous bond-formation, which is initialised through the nucleophilic attack of Padwa's carbonyl ylide on the carbonyl oxygen atom of the strongly electrophilically activated 1,2-benzoquinone. The present study allows for the establishment that along an asynchronous bond-formation, the more favourable two-center interaction begins at the most electrophilic center, which is the center with the highest spin density achieved through the charge transfer process, and not, as expected, at the center that presents the larger positive charge.

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