Document Detail

Isolation and characterization of natural allene oxides: unstable intermediates in the metabolism of lipid hydroperoxides.
MedLine Citation:
PMID:  2835769     Owner:  NLM     Status:  MEDLINE    
Allene oxides are unstable epoxides that have been implicated as intermediates in the biotransformation of hydroperoxyicosatetraenoic acids and related hydroperoxides to ketols and cyclopentenones. Direct proof of the structure of the putative allene oxide intermediates has been hampered by their extreme instability under the conditions of their biosynthesis (t1/2 approximately 15-30 sec at 0 degree C and pH 7.4). We now report the isolation and structural elucidation of allene oxides prepared from the (13S)-hydroperoxides of linoleic and linolenic acids. The compounds were biosynthesized by using a very active enzyme preparation from flaxseed. After a 5-sec incubation at 0 degrees C, the allene oxide metabolites were extracted and purified as the methyl ester derivatives at -15 degrees C. The structures were established by UV, CD, NMR, and oxygen-18 labeling experiments. 12,13(S)-Oxido-9Z,11-octadecadienoic acid is derived from linoleic acid, and 12,13(S)-oxido-9Z,11,15Z-octadecatrienoic acid is from linolenic acid. Analysis of the breakdown products formed on exposure to water led to identification of hydrolysis and cyclization products previously characterized as enzymic derivatives of the (13S)-hydroperoxides in flaxseed. Our results give direct proof of the structure of the allene oxide intermediates and should facilitate further investigation of the metabolism of this class of epoxide to prostaglandins, clavulones, and other stable end products.
A R Brash; S W Baertschi; C D Ingram; T M Harris
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Publication Detail:
Type:  Journal Article; Research Support, U.S. Gov't, P.H.S.    
Journal Detail:
Title:  Proceedings of the National Academy of Sciences of the United States of America     Volume:  85     ISSN:  0027-8424     ISO Abbreviation:  Proc. Natl. Acad. Sci. U.S.A.     Publication Date:  1988 May 
Date Detail:
Created Date:  1988-06-22     Completed Date:  1988-06-22     Revised Date:  2010-09-09    
Medline Journal Info:
Nlm Unique ID:  7505876     Medline TA:  Proc Natl Acad Sci U S A     Country:  UNITED STATES    
Other Details:
Languages:  eng     Pagination:  3382-6     Citation Subset:  IM    
Department of Pharmacology, Vanderbilt University, Nashville, TN 37232.
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MeSH Terms
Alkadienes / isolation & purification*
Drug Stability
Eicosapentaenoic Acid / analogs & derivatives*,  metabolism*
Epoxy Compounds / isolation & purification*
Ethers, Cyclic / isolation & purification*
Magnetic Resonance Spectroscopy
Molecular Conformation
Oxygen Isotopes
Grant Support
Reg. No./Substance:
0/Alkadienes; 0/Epoxy Compounds; 0/Ethers, Cyclic; 0/Oxygen Isotopes; 1553-41-9/Eicosapentaenoic Acid

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