title: Ene hydroperoxidation of isobutenylarenes within dye-exchanged zeolite Na-Y: control of site selectivity by cation-arene interactions.
abstract: The site selectivity in the singlet oxygen ene reaction of several deuterium-labeled isobutenylarenes depends on the position and the electronic nature of the aryl substitutents. For example, 1-(4-trifluoromethylphenyl)-2-methylpropene gives 82% twin selectivity whereas the isomeric 1-(2-trifluoromethylphenyl)-2-methylpropene gives 68% twix selectivity. If photooxygenation of these CF(3)-substituted compounds is carried out in solution, the opposite selectivity trends are found. On the basis of DFT calculations, these results are rationalized in terms of oxygen-cation and cation-arene interactions.
authors.affiliation: Department of Chemistry, University of Crete, 71409 Iraklion, Greece. stratakis@chemistry.uoc.gr
authors.forename: Manolis
authors.initials: M
authors.lastname: Stratakis
authors.forename: Constantinos
authors.initials: C
authors.lastname: Rabalakos
authors.forename: Giannis
authors.initials: G
authors.lastname: Mpourmpakis
authors.forename: George E
authors.initials: GE
authors.lastname: Froudakis