Model studies of β-scission ring-opening reactions of cyclohexyloxy radicals

Application to thermal rearrangements of dispiro-1,2,4-trioxanes

Stefan Erhardt, Stuart A. Macgregor, Kevin J. McCullough, Karen Savill, Benjamin J. Taylor

Research output: Contribution to journalArticle

Abstract

A DFT study of model cyclohexyloxy radicals (8a-c, 9) show that (a) the presence of an adjacent oxygen atom, and (b) a-substituents on the cyclohexyl ring, particularly methoxy, accelerate the rate of ß-scission ring-opening reactions. Consistent with theoretical results, thermolysis of the methoxy-substituted dispiro-1,2,4-trioxane 10 afforded the structurally novel, 14-membered macrocyclic keto lactone 11 as the major isolable product. © 2007 American Chemical Society.

Original languageEnglish
Pages (from-to)5569-5572
Number of pages4
JournalOrganic Letters
Volume9
Issue number26
DOIs
Publication statusPublished - 20 Dec 2007

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Lactones
Hot Temperature
Oxygen
1,2,4-trioxane

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Erhardt, Stefan ; Macgregor, Stuart A. ; McCullough, Kevin J. ; Savill, Karen ; Taylor, Benjamin J. / Model studies of β-scission ring-opening reactions of cyclohexyloxy radicals : Application to thermal rearrangements of dispiro-1,2,4-trioxanes. In: Organic Letters. 2007 ; Vol. 9, No. 26. pp. 5569-5572.
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Model studies of β-scission ring-opening reactions of cyclohexyloxy radicals : Application to thermal rearrangements of dispiro-1,2,4-trioxanes. / Erhardt, Stefan; Macgregor, Stuart A.; McCullough, Kevin J.; Savill, Karen; Taylor, Benjamin J.

In: Organic Letters, Vol. 9, No. 26, 20.12.2007, p. 5569-5572.

Research output: Contribution to journalArticle

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