环丙基作为单重态氧烯反应机理中的一种超敏探针。

The cyclopropyl group as a hypersensitive probe in the singlet oxygen ene reaction mechanism.

作者信息

Alberti Mariza N, Orfanopoulos Michael

机构信息

Department of Chemistry, University of Crete, Voutes-Heraklion, Crete, Greece.

出版信息

Org Lett. 2008 Jun 19;10(12):2465-8. doi: 10.1021/ol800759u. Epub 2008 May 20.

DOI:10.1021/ol800759u

PMID:18489176

Abstract

Cyclopropyl-substituted olefins are employed as mechanistic probes in the singlet oxygen-alkene ene reaction. In MeOH and aprotic solvents [CHCl(3), (CH(3))(2)CO, CH(3)CN], only the allylic hydroperoxides bearing an intact cyclopropyl group are detected. The reaction mechanism is independent of solvent polarity. Our findings, to a certain experimental limit, exclude a biradical or dipolar intermediate.

摘要

环丙基取代的烯烃被用作单线态氧-烯烃烯反应中的机理探针。在甲醇和非质子溶剂[CHCl₃、(CH₃)₂CO、CH₃CN]中，仅检测到带有完整环丙基的烯丙基氢过氧化物。反应机理与溶剂极性无关。在一定的实验限度内，我们的研究结果排除了双自由基或偶极中间体。