Epoxidation of trans-cyclooctene by methyltrioxorhenium/H2O2:: Reaction of trans-epoxide with the monoperoxo complex

被引：29

作者：

Adam, W ^{[1
]}

Saha-Möller, CR ^{[1
]}

Weichold, O ^{[1
]}

机构：

[1] Univ Wurzburg, Inst Organ Chem, D-97074 Wurzburg, Germany

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2000年 / 65卷 / 16期

关键词：

D O I：

10.1021/jo000564l

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The epoxidation of trans-cyclooctene (trans-1) with the MTO/H2O2, MTO/UHP, and NaY/MTO/H2O2 oxidants leads to a mixture of trans/cis-olefins 1, trans/cis-epoxides 2, and the cis-diol 3. While the oxygen transfer proceeds stereoselectively, the monoperoxo rhenium complex A, which is generated in situ during the catalytic cycle, is responsible for the facile deoxygenation, isomerization, and hydrolysis of the trans-epoxide. In the case of the homogeneous MTO/H2O2 system, rapid decomposition of the catalytically active rhenium species into HReO4 circumvents the formation of such side products. In contrast, for the heterogeneous oxidants MTO/UHP and NaY/MTO/H2O2, the catalytically active rhenium species are sufficiently stabilized and survive long enough to promote the observed side reactions.

引用

页码：5001 / 5004

页数：4

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