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.
- organofluorine chemistry
- neutral oxy-cope rearrangement
Percy, J. M., Hursthouse, M. B., Spencer, N. S., Tolley, M., DiMartino, G., & Light, M. E. (2003). Syntheses of selectively fluorinated cyclodecenones: the first deployment of the neutral oxy-cope rearrangement in organofluorine chemistry. Organic and Biomolecular Chemistry, 1(24), 4423-4434. https://doi.org/10.1039/b311261f