Synthesis of α-hydroxy-β,β-difluoro-γ-ketoesters via [3,3]sigmatropic rearrangements

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Broadhurst, Michael and Brown, Samantha J and Percy, Jonathan and Prime, Michael E (2000) Synthesis of α-hydroxy-β,β-difluoro-γ-ketoesters via [3,3]sigmatropic rearrangements. Journal of the Chemical Society, Perkin Transactions 1, 2000 (19). pp. 3217-3226. ISSN 1472-7781 (https://doi.org/10.1039/B004766J)

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Abstract

Readily available γ,γ-difluorinated allylic alcohols obtained from trifluoroethanol were esterified efficiently. Exposure to strong base (LDA) afforded the ester enolates, in which chelation both controlled configuration and stabilised against fragmentation, which were trapped as their silyl ketene acetals. Rearrangement occurred to afford base-sensitive acid products. Esterification under mild conditions afforded the purifiable methyl esters in which the masked ketone had been released. Educts with either a benzyloxy or an allyloxy group at the α-position could be deprotected releasing the alcohols.

ORCID iDs

Broadhurst, Michael, Brown, Samantha J, Percy, Jonathan ORCID logoORCID: https://orcid.org/0000-0001-8636-2704 and Prime, Michael E;
  • Item type:Article
    ID code:38921
    Dates:
    Date
    Event
    2000
    Published
    11 September 2000
    Published Online
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:03 Apr 2012 15:47
    Last modified:11 Nov 2024 10:06
    URI:https://strathprints.strath.ac.uk/id/eprint/38921
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