New cyclopentenone fatty acids formed from linoleic and linolenic acids in potato.
[1-14C]Linoleic acid was incubated with a whole homogenate preparation from potato stolons. The reaction product contained four major labeled compounds, i.e., the alpha-ketol 9-hydroxy-10-oxo-12(Z)-octadecenoic acid (59%), the epoxy alcohol 10(S),11(S)-epoxy-9(S)-hydroxy-12(Z)-octadecenoic acid (19%), the divinyl ether colneleic acid (3%), and a new cyclopentenone (13%). The structure of the last-mentioned compound was determined by chemical and spectral methods to be 2-oxo-5-pentyl-3-cyclopentene-1-octanoic acid (trivial name, 10-oxo-11-phytoenoic acid). Steric analysis demonstrated that the relative configuration of the two side chains attached to the five-membered ring was cis, and that the compound was a racemate comprising equal parts of the 9(R),13(R) and 9(S),13(S) enantiomers. Experiments in which specific trapping products of the two intermediates 9(S)-hydroperoxy-10(E),12(Z)-octadecadienoic acid and 9(S),10-epoxy-10,12(Z)-octadecadienoic acid were isolated and characterized demonstrated the presence of 9-lipoxygenase and allene oxide synthase activities in the tissue preparation used. The allene oxide generated from linoleic acid by action of these enzymes was further converted into the cyclopentenone and alpha-ketol products by cyclization and hydrolysis, respectively. Incubation of [1-14C]linolenic acid with the preparation of potato stolons afforded 2-oxo-5-[2'(Z)-pentenyl]-3-cyclopentene-1-octanoic acid (trivial name, 10-oxo-11,15(Z)-phytodienoic acid), i.e., an isomer of the jasmonate precursor 12-oxo-10,15(Z)-phytodienoic acid. Quantitative determination of 10-oxo-11-phytoenoic acid in linoleic acid-supplied homogenates of different parts of the potato plant showed high levels in roots and stolons, lower levels in developing tubers, and no detectable levels in leaves.
Hamberg
M
M
Department of Medical Biochemistry and Biophysics, Karolinska Institutet, Stockholm, Sweden. Mats.Hamberg@mbb.ki.se
D002250:Carbon Radioisotopes; D002851:Chromatography, High Pressure Liquid; D003517:Cyclopentanes / Q000032:analysis / Q000737:chemistry / Q000378:metabolism*; D005227:Fatty Acids / Q000032:analysis / Q000378:metabolism*; D008401:Gas Chromatography-Mass Spectrometry; D005979:Glutathione Peroxidase / Q000378:metabolism; D007783:Lactones / Q000378:metabolism; D019787:Linoleic Acid / Q000378:metabolism*; D008084:Lipoxygenase / Q000378:metabolism; D015394:Molecular Structure; D010084:Oxidation-Reduction; D011198:Solanum tuberosum / Q000378:metabolism*; D013056:Spectrophotometry, Ultraviolet; D017550:Spectroscopy, Fourier Transform Infrared; D013237:Stereoisomerism; D017962:alpha-Linolenic Acid / Q000378:metabolism*
D002250:Carbon Radioisotopes; D003517:Cyclopentanes; D005227:Fatty Acids; D007783:Lactones; D017962:alpha-Linolenic Acid; D019787:Linoleic Acid; D005979:Glutathione Peroxidase; D008084:Lipoxygenase; C013905:cyclopentenone