Enhanced Aromaticity of the Transition Structures for the Diels−Alder Reactions of Quinodimethanes: Evidence from ab Initio and DFT Computations

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Abstract
The Diels-Alder reactions of various quinodimethanes with ethylene are studied by means of ab initio molecular orbital and density functional theory (DFT) to show the effect of aromaticity on the reaction path. The calculations reveal that these reactions are both kinetically and thermodynamically much more favored than the prototype butadiene-ethylene Diels-Alder reaction due to the aromatization process in the transition state (TS) and product. A progressive aromaticity gain is noticed during the reaction, and hence the partial pi-delocalized peripheral diene ring function is coupled with the six-electron sigma,pi-delocalized cyclic unit resulting in an enhanced aromaticity of the TS. The magnetic criteria such as magnetic susceptibility exaltation and nucleus independent chemical shift provide definitive evidence for and fully support the aromatization process and the aromaticity of the TS. The extent of sigma-pi delocalization and the bond make-break at the TS are consistent with each other, and this is strongly influenced by the adjacent pi-aromatization process. Moreover, the aromaticity trends in the resulting TSs and products parallel the activation and reaction energies; the extent of aromatization increases with increasing reaction rate and exothermicity. This confirms that aromaticity is the driving factor governing cycloadditions involving quinodimethanes.