Characteristics of the two frontier orbital interactions in the Diels-Alder cycloaddition.
Two electron-deficient dienes were reacted with a series of twelve electron-poor and electron-rich dienophiles to give, in some cases, the corresponding Diels-Alder adducts. Clear differences in the roles played by the two frontier orbital interactions emerged. It was demonstrated that in the case of normal Diels-Alder cycloadditions, the FMO theory could predict the relative reactivities between dienophiles, while in the case of inverse-electron demand Diels-Alder reactions, it could not. It was shown that the dissymmetry in electron-rich dienophiles increases their reactivities.
Spino
Claude
C
Université de Sherbrooke, Département de Chimie, 2500 Boulevard Université, Sherbrooke, QC, Canada J1K 2R1. claude.spino@usherbrooke.ca
Rezaei
Hadi
H
Dory
Yves L
YL