An appraisal of oxoketene cycloaddition methodology for the synthesis of 2,6-dideoxysugars and fluorinated 2,6-dideoxysugars

Christophe Audouard, Kim Bettaney, Châu T. Doan, Giuseppe Rinaudo, Peter J. Jervis, Jonathan M. Percy

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9 Citations (Scopus)

Abstract

The cycloaddition reaction of acylketenes with vinyl ethers affords an extremely direct route to 2,6-dideoxysugars and their methyl ethers. The lithium enolate of commercial 2,6,6-trimethyldioxinone 3 was fluorinated in good yield to afford fluorinated dioxinone 8. An illustrative range of fluorinated 2,6-dideoxysugar derivatives was prepared via the acetyl ketene-vinyl ether cycloadduct. Electronic structure calculations were carried out to investigate the effect of the fluorine atom on ease of formation and subsequent reaction of the (fluoroacetyl) ketene reactive intermediate. A single fluorine atom lowers the barrier to fragmentation by ca. 7.5 kJ mol(-1), consistent with experimental findings, but has almost no effect on the barrier to rate determining vinyl ether addition, or to oxoketene dimerisation.
Original languageEnglish
Pages (from-to)1573-1582
Number of pages9
JournalOrganic and Biomolecular Chemistry
Volume7
Issue number8
DOIs
Publication statusPublished - 2009

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Keywords

  • conjugated ketenes
  • deoxy sugars
  • landomycin
  • chemistry
  • stereoselectivity
  • formadimine
  • substituents
  • vinylketene

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