TY - JOUR
T1 - The role of supramolecular intermediates in the potential energy surface of the Diels-Alder reaction
AU - Ramírez-Gualito, Karla
AU - López-Mora, Néstor
AU - Jiménez-Vázquez, Hugo A.
AU - Tamariz, Joaquín
AU - Cuevas, Gabriel
PY - 2013/10
Y1 - 2013/10
N2 - 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.
AB - 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.
KW - Diels-alder reaction
KW - Dispersion forces
KW - Interaction energies
KW - Reaction mechanism
KW - Van der waals complex
UR - http://www.scopus.com/inward/record.url?scp=84892724006&partnerID=8YFLogxK
M3 - Artículo
SN - 1870-249X
VL - 57
SP - 267
EP - 275
JO - Journal of the Mexican Chemical Society
JF - Journal of the Mexican Chemical Society
IS - 4
ER -