Thermal conversions of fatty acid peroxides to cyclopentenones: a biomimetic model for allene oxide synthase pathway.

The trimethylsilyl (TMS) peroxides of linoleic acid 9(S)-hydroperoxide (TMS or Me esters) were subjected to gas chromatography-mass spectrometry (GC-MS) analyses. The cyclopentenones, trans- and cis-10-oxo-11-phytoenoic acid (10-oxo-PEA, Me or TMS esters) were first time detected as the products of TMS-peroxide thermal conversions. The major products were ketodienes, epoxyalcohols, hemiacetals and decadienals. For further study of thermal cyclopentenone formation, 9(S)- or 13(S)-hydroperoxides of linoleic acid (Me esters) were sealed in ampoules and heated at 230 °C for 15 or 30 min. The products were separated by HPLC. The cyclopentenone fractions were collected and analyzed by GC-MS. Trans-10-oxo-PEA (Me) and 10-oxo-9(13)-PEA (Me) were formed during the thermal conversion of 9-hydroperoxide (Me ester). Similarly, the cyclopentenones trans-12-oxo-PEA (Me) and 12-oxo-9(13)-PEA (Me) were detected after the heating of 13-hydroperoxide (Me ester). Thermal formation of cyclopentenones can be considered as a biomimetic model of AOS pathway, providing new insights into the mechanisms of allene oxide formation and cyclization.