title: A density functional theory study on the electrocyclization of 1,2,4,6-heptatetraene analogues: converting a pericyclic to a pseudopericyclic reaction.
abstract: A comprehensive B3LYP/6-31+G* study on the electrocyclization of 1,2,4,6-heptatetraene analogues was conducted. Starting from the cyclization of (2Z)-2,4,5-hexatrienal, a pericyclic disrotatory process favored by the assistance of a electron lone pair, we incorporated small modifications in its molecular structure to obtain a truly pseudopericyclic process. To this purpose electronegative atoms (fluorine and nitrogen) were added to give a more electrophilic character on the carbon atom which is attacked by the electron lone pair of the oxygen atom. The complete pathway for each reaction was determined, and changes in magnetic properties were monitored with a view to estimating the aromatization associated with each process. This information, together with the energetic and structural results, allowed us to classify the reactions as pseudopericyclic or pericyclic. Among all studied reactions only one was a truly pseudopericyclic process and another was a borderline case. The features of this unequivocally pseudopericyclic case were analyzed in depth.
authors.affiliation: Departamento de Química Física, Facultade de Ciencias, Universidade de Santiago, Campus de Lugo, Avda. Alfonso X El Sabio s/n, 27002 Lugo, Spain.
authors.forename: Enrique M
authors.initials: EM
authors.lastname: Cabaleiro-Lago
authors.forename: Jesús
authors.initials: J
authors.lastname: Rodríguez-Otero
authors.forename: Rosa M
authors.initials: RM
authors.lastname: García-López
authors.forename: Angeles
authors.initials: A
authors.lastname: Peña-Gallego
authors.forename: Jose M
authors.initials: JM
authors.lastname: Hermida-Ramón