The Peroxide Changes Everything: New Methodology for the Synthesis of Peroxide-containing Natural Products

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Abstract

This account describes the evolution of a synthetic program from initial investigations of the stability of peroxide protecting groups to the use of peroxides as mediators of C-C bond-forming reactions. The stability of monoperoxyketals towards olefinations and organometallic additions allows a new approach to peroxide synthesis based upon formation of C-C or C=C bonds in the presence of protected hydroperoxides, a strategy which has been successfully applied to the synthesis of the unstable eicosanoids 15(S)-HPETE and 5(S)-HPETE. Peroxyketals are also capable of mediating C-C bond formation; ionization of peroxyketals in the presence of Lewis acids produces peroxycarbenium ion intermediates able to undergo both inter- and intramolecular trapping with electron-rich alkenes. The lack of enantioselective approaches to peroxide-containing synthons continues to impose a serious constraint on our approaches to peroxide natural products and the account closes with a discussion of new methods for asymmetric chemical peroxidation.

Original languageEnglish (US)
Pages (from-to)997-1003
Number of pages7
JournalSynlett
Volume1995
Issue number10
DOIs
Publication statusPublished - Oct 1995

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Keywords

  • HPETE
  • hydroperoxide
  • monoperoxyketal
  • peroxide
  • peroxycarbenium

ASJC Scopus subject areas

  • Organic Chemistry

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