Auxiliary-directed peroxidation of 1,4-dienes

Patrick H. Dussault, Todd A. Anderson, Michael R. Hayden, Kevin J. Koeller, Q. Jason Niu

Research output: Contribution to journalArticle

4 Scopus citations

Abstract

The addition of singlet oxygen (1O2) to the proximal alkene of auxiliary-tethered 1,4-dienes and the addition of triplet oxygen 3O2) to the proximal position of the corresponding pentadienyl radicals both produce conjugated diene hydroperoxides in moderate to high diastereomeric excess. Negligible stereoselection is observed for additions of 1O2 to the distal alkene of Z,Z-heptadienes due to the lack of control of alkene conformation. Despite evidence for the intermediacy of highly constrained pentadienyl radicals, poor diastereoselection is also observed for distal addition of 3O2. The extent of olefin isomerization observed during radical oxygenations can be correlated with steric constraints on the intermediate pentadienyl and peroxyl radicals and may be relevant to literature reports of olefin isomerization during enzymatic oxygenations of unnatural fatty acids.

Original languageEnglish (US)
Pages (from-to)12381-12398
Number of pages18
JournalTetrahedron
Volume52
Issue number38
DOIs
Publication statusPublished - Sep 16 1996

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Keywords

  • chiral auxiliary
  • diene
  • hydroperoxide
  • oxygenation
  • singlet oxygen

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

Cite this

Dussault, P. H., Anderson, T. A., Hayden, M. R., Koeller, K. J., & Jason Niu, Q. (1996). Auxiliary-directed peroxidation of 1,4-dienes. Tetrahedron, 52(38), 12381-12398. https://doi.org/10.1016/0040-4020(96)00744-2