Rapid intramolecular 1,4-hydride transfer across a rigid 4-hydroxycycloheptanone

Robert Cernik, Gabrielle Anne Craze, Owen S Mills, Ian Watt

    Research output: Contribution to journalArticlepeer-review


    The 13C NMR of hydroxy ketone I (R = Na) was temp. dependent, behavior assocd. with rapid degenerate rearrangement involving intramol. hydride transfer from alkoxide to CO. Dynamic 13C NMR measurements gave a barrier to rearrangement of 13.7 kcal/mol at 4°. A much slower competing process giving hemiacetal II was obsd., and the mechanism of its formation is discussed. The mol. structure of I (R = p-O2NC6H4), detd. by x-ray crystallog., shows some pyramidalization for the ketonic CO group. [on SciFinder(R)]
    Original languageEnglish
    Pages (from-to)361-7
    Number of pages353
    JournalJ. Chem. Soc., Perkin Trans. 2
    Issue number3
    Publication statusPublished - 1982


    • Nuclear magnetic resonance (of carbon-13, in hydroxypentacyclododecanone and its derivs.)
    • Rearrangement (of hydroxypentacyclododecanone, hemiacetal by intramol.)
    • Crystal structure
    • Molecular structure (of pentacyclododecanonyl nitrobenzoate)
    • furanylpentacyclododecane
    • hemiacetal hydroxypentacyclododecanone intramol
    • rearrangement hydroxypentacyclododecanone
    • hydroxycycloheptanone intramol hydride transfer
    • cycloheptane hydroxy intramol hydride transfer
    • pentacyclododecanonyl nitrobenzoate crystal mol structure
    • NMR carbon 13 hydroxypentacyclododecanone


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