Syntheses of selectively fluorinated cyclodecenones: the first deployment of the neutral oxy-cope rearrangement in organofluorine chemistry

J.M. Percy, M.B. Hursthouse, N.S. Spencer, M. Tolley, G. DiMartino, M.E. Light

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Metallated haloalkenes were used to open epoxides in moderate to good yield. The homoallylic alcohols obtained underwent Swern oxidation to afford three γ,γ-difluorinated β,γ-enones, which reacted with either vinyllithium, 2-lithio-2H-dihydropyran or another metallated haloalkene to afford substituted trans-1,2-divinylcyclohexanols of different degrees of stability. These intermediates underwent neutral thermal oxy-Cope rearrangements when heated in xylene in Ace® tubes. The first-formed enols ketonised without loss of HF to afford a range of cyclodecenones in moderate to good yield; X-ray crystallography was used extensively for product characterisation. All substrates rearranged more rapidly than a cis/trans mixture of 1,2-divinylcyclohexanols.
LanguageEnglish
Pages4423-4434
Number of pages12
JournalOrganic and Biomolecular Chemistry
Volume1
Issue number24
DOIs
Publication statusPublished - 2003

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Xylenes
X ray crystallography
X Ray Crystallography
Epoxy Compounds
Hot Temperature
Alcohols
chemistry
Oxidation
epoxy compounds
xylene
Substrates
synthesis
crystallography
alcohols
tubes
oxidation
products
x rays

Keywords

  • cyclodecenones
  • organofluorine chemistry
  • neutral oxy-cope rearrangement

Cite this

Percy, J.M. ; Hursthouse, M.B. ; Spencer, N.S. ; Tolley, M. ; DiMartino, G. ; Light, M.E. / Syntheses of selectively fluorinated cyclodecenones: the first deployment of the neutral oxy-cope rearrangement in organofluorine chemistry. In: Organic and Biomolecular Chemistry. 2003 ; Vol. 1, No. 24. pp. 4423-4434.
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Syntheses of selectively fluorinated cyclodecenones: the first deployment of the neutral oxy-cope rearrangement in organofluorine chemistry. / Percy, J.M.; Hursthouse, M.B.; Spencer, N.S.; Tolley, M.; DiMartino, G.; Light, M.E.

In: Organic and Biomolecular Chemistry, Vol. 1, No. 24, 2003, p. 4423-4434.

Research output: Contribution to journalArticle

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AU - Percy, J.M.

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AB - Metallated haloalkenes were used to open epoxides in moderate to good yield. The homoallylic alcohols obtained underwent Swern oxidation to afford three γ,γ-difluorinated β,γ-enones, which reacted with either vinyllithium, 2-lithio-2H-dihydropyran or another metallated haloalkene to afford substituted trans-1,2-divinylcyclohexanols of different degrees of stability. These intermediates underwent neutral thermal oxy-Cope rearrangements when heated in xylene in Ace® tubes. The first-formed enols ketonised without loss of HF to afford a range of cyclodecenones in moderate to good yield; X-ray crystallography was used extensively for product characterisation. All substrates rearranged more rapidly than a cis/trans mixture of 1,2-divinylcyclohexanols.

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