Abstract
[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 α-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 α-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.
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Abbreviations
- 9-H(P)OD:
-
9-hydro(pero)xy-10(E), 12(Z)-octadecadienoic acid
- 9-H(P)OT:
-
9-hydro(pero)xy-10(E), 12(Z), 15(Z)-octadecatrienoic acid
- 12-oxo-PDA:
-
12-oxo-10, 15(Z)-phytodienoic acid {4-oxo-5-[2′(Z)-pentenyl]-2-cyclopentene-1-octanoic acid}
- 12-oxo-PEA:
-
12-oxo-10-phytoenoic acid [4-oxo-5-pentyl-2-cyclopentene-1-octanoic acid]
- 13-H(P)OD:
-
13-hydro(pero)xy-9(Z), 11(E)-octadecadienoic acid
- 13-H(P)OT:
-
13-hydro(pero)xy-9(Z), 11(E), 15(Z)-octadecatrienoic acid
- AOS:
-
allene oxide synthase
- colneleic acid:
-
9-[1′(E),3′(Z)-nonadienyloxy]-8(E)-nonenoic acid
- colnelenic acid:
-
9-[1′(E),3′(Z),6′(Z)-nonatrienyloxy]-8(E)-nonenoic acid
- CP-HPLC:
-
chiral-phase high-performance liquid chromatography
- FTIR:
-
Fourier transform infrared
- GC-MS:
-
gas chromatography-mass spectrometry
- GLC:
-
gas-liquid chromatography
- GSH:
-
reduced glutathione
- GSH-px:
-
glutathione peroxidase
- MC:
-
(−)-menthoxycarbonyl
- NMR:
-
nuclear magnetic resonance
- RP-HPLC:
-
reversed-phase high-performance liquid chromatography
- SP-HPLC:
-
straight-phase high-performance liquid chromatography
- UV:
-
ultraviolet
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Hamberg, M. New cyclopentenone fatty acids formed from linoleic and linolenic acids in potato. Lipids 35, 353–363 (2000). https://doi.org/10.1007/s11745-000-532-z
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DOI: https://doi.org/10.1007/s11745-000-532-z