Stereospecific removal of the pro-R hydrogen at C-8 of (9S)-hydroperoxyoctadecadienoic acid in the biosynthesis of colneleic acid

The stereochemistry of hydrogen removal in the conversion of (9S)-hydroperoxyoctadeca-(10E, 12Z)-dienoic acid (2) into colneleic acid (4) was studied. [(8R)-2H]-(2) and [(8S)-2H]-(2) were incubated with the 105 000g particle fraction of potato homogenate and the colneleic acid formed was isolated. Mass spectrometric analysis demonstrated that colneleic acid which was biosynthesized from the [(8R)-2H]-hydroperoxide was largely devoid of deuterium, whereas colneleic acid produced from the [(8S)-2H]-hydroperoxide retained most of the deuterium. Accordingly, there is a selective removal of the pro-R hydrogen at C-8 in the biosynthesis of colneleic acid from (9S)-hydroperoxyoctadeca-(10E, 12Z)-dienoic acid.

[1]  M. Hamberg.  Mechanism of corn hydroperoxide isomerase: detection of 12,13(S)-oxido-9(Z),11-octadecadienoic acid , 1987 .

[2]  M. Hamberg.  Omega 6-oxygenation of 6, 9, 12-octadecatrienoic acid in human platelets. , 1983, Biochemical and biophysical research communications.

[3]  M. Hamberg,et al.  On the mechanism of biosynthesis of leukotrienes and related compounds , 1982, FEBS letters.

[4]  M. Hamberg,et al.  On the mechanism of the oxygenation of arachidonic acid by human platelet lipoxygenase. , 1980, Biochemical and biophysical research communications.

[5]  M. Hamberg.  Transformations of 5,8,11,14,17-eicosapentaenoic acid in human platelets. , 1980, Biochimica et biophysica acta.

[6]  D. Weisleder,et al.  Oxygenated fatty acids of isano oil , 1977 .

[7]  T. Galliard,et al.  The enzymic and non-enzymic degradation of colneleic acid, an unsaturated fatty acid ether intermediate in the lipoxygenase pathway of linoleic acid oxidation in potato (Solanum tuberosum) tubers. , 1974, The Biochemical journal.

[8]  D. Phillips,et al.  Novel divinyl ether fatty acids in extracts of Solanum tuberosum , 1973 .

[9]  D. Phillips,et al.  The enzymic conversion of linoleic acid into 9-(nona-1',3'-dienoxy)non-8-enoic acid, a novel unsaturated ether derivative isolated from homogenates of Solanum tuberosum tubers. , 1972, The Biochemical journal.

[10]  M. Hamberg.  Steric analysis of hydroperoxides formed by lipoxygenase oxygenation of linoleic acid. , 1971, Analytical biochemistry.

[11]  D. Phillips,et al.  Lipoxygenase from potato tubers. Partial purification and properties of an enzyme that specifically oxygenates the 9-position of linoleic acid. , 1971, The Biochemical journal.

[12]  M. Hamberg,et al.  On the mechanism of the biosynthesis of prostaglandins E-1 and F-1-alpha. , 1967, The Journal of biological chemistry.

[13]  M. Hamberg,et al.  Oxygenation of unsaturated fatty acids by the vesicular gland of sheep. , 1967, The Journal of biological chemistry.

[14]  K. Bloch,et al.  THE STEREOSPECIFIC CONVERSION OF STEARIC ACID TO OLEIC ACID. , 1965, The Journal of biological chemistry.