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

被引:20
作者
Stratakis, M [1 ]
Rabalakos, C [1 ]
Mpourmpakis, G [1 ]
Froudakis, GE [1 ]
机构
[1] Univ Crete, Dept Chem, Iraklion 71409, Greece
关键词
D O I
10.1021/jo020599g
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
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.
引用
收藏
页码:2839 / 2843
页数:5
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