Regioselective radical cyclization initiated by the reaction of allylic hydroperoxides with iron(II) sulfate

Araki Masuyama, Tomohiro Sugawara, Masatomo Nojima, Kevin J. McCullough

Research output: Contribution to journalArticle

Abstract

Treatment of 1-methyl-2-methylene-1-cyclohexyl hydroperoxide with a mixture of FeSO4/CuCl2 yielded 1-(1-chlorocyclohexyl)ethanone as the major product consistent with 6-endo-trig cyclization of the intermediate 5-acetylhex-5-enyl radical. This strategy was extended to the ring enlargement of a series of 1-isopropenylcycloalkyl hydroperoxides. Regioselective 7- or 8-endo-trig cyclization reactions could be achieved by treatment of the corresponding cyclopentyl or cyclohexyl hydroperoxides with either a mixture of FeSO4/CuCl2 or with FeSO4 only. The influence of substituents on the efficiency of the 8-endo-trig cyclization process was also explored. © 2003 Published by Elsevier Science Ltd.

Original languageEnglish
Pages (from-to)353-366
Number of pages14
JournalTetrahedron
Volume59
Issue number3
DOIs
Publication statusPublished - 13 Jan 2003

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Cyclization
Hydrogen Peroxide
Sulfates
Iron
cupric chloride

Keywords

  • Allylic hydroperoxide
  • endo-trig radical cyclization
  • Iron(II) sulfate
  • Ring enlargement

Cite this

Masuyama, Araki ; Sugawara, Tomohiro ; Nojima, Masatomo ; McCullough, Kevin J. / Regioselective radical cyclization initiated by the reaction of allylic hydroperoxides with iron(II) sulfate. In: Tetrahedron. 2003 ; Vol. 59, No. 3. pp. 353-366.
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Regioselective radical cyclization initiated by the reaction of allylic hydroperoxides with iron(II) sulfate. / Masuyama, Araki; Sugawara, Tomohiro; Nojima, Masatomo; McCullough, Kevin J.

In: Tetrahedron, Vol. 59, No. 3, 13.01.2003, p. 353-366.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Regioselective radical cyclization initiated by the reaction of allylic hydroperoxides with iron(II) sulfate

AU - Masuyama, Araki

AU - Sugawara, Tomohiro

AU - Nojima, Masatomo

AU - McCullough, Kevin J.

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AB - Treatment of 1-methyl-2-methylene-1-cyclohexyl hydroperoxide with a mixture of FeSO4/CuCl2 yielded 1-(1-chlorocyclohexyl)ethanone as the major product consistent with 6-endo-trig cyclization of the intermediate 5-acetylhex-5-enyl radical. This strategy was extended to the ring enlargement of a series of 1-isopropenylcycloalkyl hydroperoxides. Regioselective 7- or 8-endo-trig cyclization reactions could be achieved by treatment of the corresponding cyclopentyl or cyclohexyl hydroperoxides with either a mixture of FeSO4/CuCl2 or with FeSO4 only. The influence of substituents on the efficiency of the 8-endo-trig cyclization process was also explored. © 2003 Published by Elsevier Science Ltd.

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