The role of supramolecular intermediates in the potential energy surface of the Diels-Alder reaction

Karla Ramírez-Gualito, Néstor López-Mora, Hugo A. Jiménez-Vázquez, Joaquín Tamariz, Gabriel Cuevas

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Abstract

The potential energy surface of four stereoselective Diels-Alder reactions was studied, namely: cyclopentadiene-maleic anhydride, furan-maleic anhydride, the dimerization of cyclopentadiene, and cyclopentadiene-cyclopropene. For completeness, we also studied the reaction between ethylene and 2-hydroxy-6-methyl-1,4-benzoqui-none, a [5+2] cycloaddition reaction. For all cases at least a stationary state of supramolecular nature a van der Waals complex, was determined. These stationary states are complexes formed by the interaction between the reagents, minima located in the paths between the non-interacting molecules and the transition states. The existence of these complexes makes it necessary to reconsider the role of Secondary Orbital Interactions in the selectivity of these reactions. As it is the case with other complexes, the stability of these supramolecular intermediates depends on electrostatic phenomena such as dispersion forces. The observation of [5+2] intramolecular complexes in solution is important since up to now, this kind of van der Waals complexes had only been described in the gas phase. © 2013, Sociedad Química de México.
Original languageAmerican English
Pages (from-to)267-275
Number of pages239
JournalJournal of the Mexican Chemical Society
StatePublished - 1 Oct 2013

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Cyclopentanes
Potential energy surfaces
Maleic Anhydrides
Cycloaddition
Dimerization
Electrostatics
Gases
Molecules

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title = "The role of supramolecular intermediates in the potential energy surface of the Diels-Alder reaction",
abstract = "The potential energy surface of four stereoselective Diels-Alder reactions was studied, namely: cyclopentadiene-maleic anhydride, furan-maleic anhydride, the dimerization of cyclopentadiene, and cyclopentadiene-cyclopropene. For completeness, we also studied the reaction between ethylene and 2-hydroxy-6-methyl-1,4-benzoqui-none, a [5+2] cycloaddition reaction. For all cases at least a stationary state of supramolecular nature a van der Waals complex, was determined. These stationary states are complexes formed by the interaction between the reagents, minima located in the paths between the non-interacting molecules and the transition states. The existence of these complexes makes it necessary to reconsider the role of Secondary Orbital Interactions in the selectivity of these reactions. As it is the case with other complexes, the stability of these supramolecular intermediates depends on electrostatic phenomena such as dispersion forces. The observation of [5+2] intramolecular complexes in solution is important since up to now, this kind of van der Waals complexes had only been described in the gas phase. {\circledC} 2013, Sociedad Qu{\'i}mica de M{\'e}xico.",
author = "Karla Ram{\'i}rez-Gualito and N{\'e}stor L{\'o}pez-Mora and Jim{\'e}nez-V{\'a}zquez, {Hugo A.} and Joaqu{\'i}n Tamariz and Gabriel Cuevas",
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The role of supramolecular intermediates in the potential energy surface of the Diels-Alder reaction. / Ramírez-Gualito, Karla; López-Mora, Néstor; Jiménez-Vázquez, Hugo A.; Tamariz, Joaquín; Cuevas, Gabriel.

In: Journal of the Mexican Chemical Society, 01.10.2013, p. 267-275.

Research output: Contribution to journalArticle

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