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Synlett 1995; 1995(10): 997-1003
DOI: 10.1055/s-1995-5154
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The Peroxide Changes Everything: New Methodology for the Synthesis of Peroxide-containing Natural Products

Pat Dussault*
  • *Department of Chemistry, University of Nebraska-Lincoln, Lincoln, NE 68588-0304, USA, FAX (402) 472-9402, internet: dussault@unlinfo.unl.edu
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Publication History

Publication Date:
31 December 2000 (online)

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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.

peroxide - hydroperoxide - monoperoxyketal - HPETE - peroxycarbenium