Ene hydroperoxidation of isobutenylarenes within dye-exchanged zeolite Na-Y: control of site selectivity by cation-arene interactions

J Org Chem. 2003 Apr 4;68(7):2839-43. doi: 10.1021/jo020599g.


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.