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

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2003年 / 68卷 / 07期

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.

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收藏

页码：2839 / 2843

页数：5

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