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

Michael Broadhurst, Samantha J Brown, Jonathan Percy, Michael E Prime

Research output: Contribution to journalArticle

28 Citations (Scopus)
37 Downloads (Pure)

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.
Original languageEnglish
Pages (from-to)3217-3226
Number of pages10
JournalJournal of the Chemical Society, Perkin Transactions 1
Volume2000
Issue number19
Early online date11 Sep 2000
DOIs
Publication statusPublished - 2000

Keywords

  • trifluoroethanol
  • allylic alcohols
  • fragmentation
  • benzyloxy
  • allyloxy

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