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Ene Hydroperoxidation of Isobutenylarenes within Dye-Exchanged Zeolite Na−Y: Control of Site Selectivity by Cation−Arene Interactions

2003; American Chemical Society; Volume: 68; Issue: 7 Linguagem: Inglês

10.1021/jo020599g

1520-6904

Manolis Stratakis, Constantinos Rabalakos, Giannis Mpourmpakis, George E. Froudakis,

Advanced Chemical Physics Studies

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 CF3-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.