Understanding the influence of Lewis acids in the regioselectivity of the Diels-Alder reactions of 2-methoxy-5-methyl-1,4-benzoquinone: A DFT study

Jorge Soto-Delgado, Luis R. Domingo, Renato Contreras

Resultado de la investigación: Article

10 Citas (Scopus)

Resumen

The mechanisms of the Diels-Alder (DA) reactions of 2-methoxy-5-methyl-1,4-benzoquinone 1 with 2-methyl-1,3-butadiene 2, in the absence and in the presence of LA catalysts, have been studied using the DFT method at the B3LYP/6-31G(d) level of theory. The uncatalyzed DA reactions between 1 and 2 take place via synchronous concerted TSs. The large activation barrier as well as the low stereo and regioselectivity associated with the uncatalyzed process are in clear agreement with the non-polar character of the cycloaddition. Coordination of the LA catalysts, BF3 or SnCl4, to the oxygen atoms of the benzoquinone 1 produces a large acceleration of the reaction, which can be associated with the large polar character of the cycloaddition. The different coordination modes of BF3 and SnCl4 LA catalysts to the oxygen atoms of benzoquinone 1 allow explaining the reverse para/meta regioselectivity observed in these LA-catalyzed DA reactions. The analysis based on the global and local electrophilicity indices of the reagents correctly explains the polar nature of the title reactions, as well as the change of regioselectivity experimentally observed.

Idioma originalEnglish
Páginas (desde-hasta)103-108
Número de páginas6
PublicaciónJournal of Molecular Structure: THEOCHEM
Volumen902
N.º1-3
DOI
EstadoPublished - 30 may 2009

Huella dactilar

Lewis Acids
Regioselectivity
Diels-Alder reactions
Cycloaddition Reaction
quinones
Discrete Fourier transforms
Cycloaddition
cycloaddition
catalysts
acids
Catalysts
oxygen atoms
Oxygen
Atoms
butadiene
reagents
Chemical activation
activation
2-methoxy-5-methyl-1,4-benzoquinone
benzoquinone

ASJC Scopus subject areas

  • Biochemistry
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Citar esto

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title = "Understanding the influence of Lewis acids in the regioselectivity of the Diels-Alder reactions of 2-methoxy-5-methyl-1,4-benzoquinone: A DFT study",
abstract = "The mechanisms of the Diels-Alder (DA) reactions of 2-methoxy-5-methyl-1,4-benzoquinone 1 with 2-methyl-1,3-butadiene 2, in the absence and in the presence of LA catalysts, have been studied using the DFT method at the B3LYP/6-31G(d) level of theory. The uncatalyzed DA reactions between 1 and 2 take place via synchronous concerted TSs. The large activation barrier as well as the low stereo and regioselectivity associated with the uncatalyzed process are in clear agreement with the non-polar character of the cycloaddition. Coordination of the LA catalysts, BF3 or SnCl4, to the oxygen atoms of the benzoquinone 1 produces a large acceleration of the reaction, which can be associated with the large polar character of the cycloaddition. The different coordination modes of BF3 and SnCl4 LA catalysts to the oxygen atoms of benzoquinone 1 allow explaining the reverse para/meta regioselectivity observed in these LA-catalyzed DA reactions. The analysis based on the global and local electrophilicity indices of the reagents correctly explains the polar nature of the title reactions, as well as the change of regioselectivity experimentally observed.",
keywords = "Benzoquinones, Diels-Alder reactions, Lewis acids, Regioselectivity, Transition states",
author = "Jorge Soto-Delgado and Domingo, {Luis R.} and Renato Contreras",
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TY - JOUR

T1 - Understanding the influence of Lewis acids in the regioselectivity of the Diels-Alder reactions of 2-methoxy-5-methyl-1,4-benzoquinone

T2 - A DFT study

AU - Soto-Delgado, Jorge

AU - Domingo, Luis R.

AU - Contreras, Renato

PY - 2009/5/30

Y1 - 2009/5/30

N2 - The mechanisms of the Diels-Alder (DA) reactions of 2-methoxy-5-methyl-1,4-benzoquinone 1 with 2-methyl-1,3-butadiene 2, in the absence and in the presence of LA catalysts, have been studied using the DFT method at the B3LYP/6-31G(d) level of theory. The uncatalyzed DA reactions between 1 and 2 take place via synchronous concerted TSs. The large activation barrier as well as the low stereo and regioselectivity associated with the uncatalyzed process are in clear agreement with the non-polar character of the cycloaddition. Coordination of the LA catalysts, BF3 or SnCl4, to the oxygen atoms of the benzoquinone 1 produces a large acceleration of the reaction, which can be associated with the large polar character of the cycloaddition. The different coordination modes of BF3 and SnCl4 LA catalysts to the oxygen atoms of benzoquinone 1 allow explaining the reverse para/meta regioselectivity observed in these LA-catalyzed DA reactions. The analysis based on the global and local electrophilicity indices of the reagents correctly explains the polar nature of the title reactions, as well as the change of regioselectivity experimentally observed.

AB - The mechanisms of the Diels-Alder (DA) reactions of 2-methoxy-5-methyl-1,4-benzoquinone 1 with 2-methyl-1,3-butadiene 2, in the absence and in the presence of LA catalysts, have been studied using the DFT method at the B3LYP/6-31G(d) level of theory. The uncatalyzed DA reactions between 1 and 2 take place via synchronous concerted TSs. The large activation barrier as well as the low stereo and regioselectivity associated with the uncatalyzed process are in clear agreement with the non-polar character of the cycloaddition. Coordination of the LA catalysts, BF3 or SnCl4, to the oxygen atoms of the benzoquinone 1 produces a large acceleration of the reaction, which can be associated with the large polar character of the cycloaddition. The different coordination modes of BF3 and SnCl4 LA catalysts to the oxygen atoms of benzoquinone 1 allow explaining the reverse para/meta regioselectivity observed in these LA-catalyzed DA reactions. The analysis based on the global and local electrophilicity indices of the reagents correctly explains the polar nature of the title reactions, as well as the change of regioselectivity experimentally observed.

KW - Benzoquinones

KW - Diels-Alder reactions

KW - Lewis acids

KW - Regioselectivity

KW - Transition states

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