Abstract

AbstractLipoxygenases (LOX) catalyse allylic oxidations and epoxidations of a co‐substrate in the presence of an unsaturated fatty acid containing a 1,4‐pentadiene moiety. One‐ and two‐step enzyme assays were established to verify the role or involvement of LOX in such co‐oxidations. It was shown that LOX is only involved in the formation of reactive hydroperoxides, but not in the oxidation of a co‐substrate, assuming a mechanism involving free peroxy radicals for the latter. Ten mono‐ and sesquiterpenes were used as co‐substrates and the resulting products were analysed by mass spectrometry. A semi‐preparative approach was developed using (+)‐valencene as an example, and the resulting products were isolated by preparative GC and their structures elucidated by NMR spectroscopy.

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