Studying Double Group Transfer Reactions by Means of Computational Methods

Israel      Fernandez; Fernando      P. Cossio

doi:10.2174/138527210793563242

Abstract

In this article, recent computational studies focused on double group transfer reactions and related processes are summarized. The reported results clearly indicate that these transformations can be considered as a subclass of pericyclic reactions occurring concertedly, with high activation barriers and synchronicity values, and through highly symmetric transition states. Interestingly, the aromatic nature of the latter saddle points has been also studied and discussed showing that they can be viewed as the in-plane analogues of sixmembered hetero-aromatic rings. Finally, the application of the so-called “Strain Model” on these important processes has demonstrated that the strain (the energy required to deform the reactants to the geometry they present in the corresponding transition state) is the major factor controlling the high barrier heights in spite of the stabilizing contribution of the aromaticity.

Keywords: Double Group Transfer Reactions, Pericyclic Reactions, Aromaticity, Quantum Chemical Calculations, Activation Strain Model, Dyotropic Reactions, Computational Methods, Woordward and Hoffmann rules, Electrophile- nucleophile interactions, Meerwein-Ponndorf-Verley reduction (MPV) of carbonyl groups, Nuclear Independent Chemical Shifts (NICS), Anisotropy of the Induced Current Density (AICD) method, Frontier molecular orbitals (FMO's), Inplane analogues of six-membered heteroaromatic rings, Computed Intrinsic Reaction Coordinate (IRC), HOMO-LUMO interactions, Valence Bond (VB) techniques