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

Syntheses of selectively fluorinated cyclodecenones: the first deployment of the neutral oxy-Cope rearrangement in organofluorine chemistry
Syntheses of selectively fluorinated cyclodecenones: the first deployment of the neutral oxy-Cope rearrangement in organofluorine chemistry
Metallated haloalkenes were used to open epoxides in moderate to good yield. The homoallylic alcohols obtained underwent Swern oxidation to afford three ??-difluorinated ?,?-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(R) 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.
1477-0520
4361-4470
DiMartino, Gianluca
c8a11c2b-7381-4fc6-8883-a94fb9727cc3
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Percy, Jonathan M.
2e5ad3da-e361-4521-a28f-acb97e4e9118
Spencer, Neil S.
3787cd69-8ab5-4557-b601-4fd3a7789240
Tolley, Malcolm
b9073b7b-7fa4-4230-8dbc-b7dc8810059b
DiMartino, Gianluca
c8a11c2b-7381-4fc6-8883-a94fb9727cc3
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Percy, Jonathan M.
2e5ad3da-e361-4521-a28f-acb97e4e9118
Spencer, Neil S.
3787cd69-8ab5-4557-b601-4fd3a7789240
Tolley, Malcolm
b9073b7b-7fa4-4230-8dbc-b7dc8810059b

DiMartino, Gianluca, Hursthouse, Michael B., Light, Mark E., Percy, Jonathan M., Spencer, Neil S. and Tolley, Malcolm (2003) Syntheses of selectively fluorinated cyclodecenones: the first deployment of the neutral oxy-Cope rearrangement in organofluorine chemistry. Organic & Biomolecular Chemistry, 1 (24), 4361-4470. (doi:10.1039/b311261f).

Record type: Article

Abstract

Metallated haloalkenes were used to open epoxides in moderate to good yield. The homoallylic alcohols obtained underwent Swern oxidation to afford three ??-difluorinated ?,?-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(R) 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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Published date: 2003

Identifiers

Local EPrints ID: 39107
URI: https://eprints.soton.ac.uk/id/eprint/39107
ISSN: 1477-0520
PURE UUID: 53242297-047b-41a9-a6f4-c012331ee51f
ORCID for Mark E. Light: ORCID iD orcid.org/0000-0002-0585-0843

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Date deposited: 21 Jun 2006
Last modified: 20 Jul 2019 01:10

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Contributors

Author: Gianluca DiMartino
Author: Mark E. Light ORCID iD
Author: Jonathan M. Percy
Author: Neil S. Spencer
Author: Malcolm Tolley

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