Jasmonic acid is not a biosynthetic intermediate to produce the pyrethrolone moiety in pyrethrin II
Ryo Matsui, Kisumi Takiguchi, Naoshige Kuwata, Katsunari Oki, Kosaku Takahashi, Kazuhiko Matsuda, Hideyuki Matsuura
Abstract
Abstract Pyrethrum ( Tanacetum cinerariifolium ) produces insecticidal compounds known as pyrethrins. Pyrethrins are esters; the acid moiety is either trans -chrysanthemic acid or pyrethric acid and the alcohol moiety of pyrethrins is either pyrethrolone, cinerolone, or jasmolone. It was generally accepted that cis -jasmone was biosynthetic intermediate to produce the alcohol moieties of pyrethrin, and the biosynthetic origin of the ci s-jasmone was postulated to be jasmonic acid. However, there was no direct evidence to prove this hypothesis. In order to uncover the origin of pyrethrolone moiety in pyrethrin II, feeding experiments were performed employing deuterium- and 13 C-labeled compounds as substrates, and the expected labeled compounds were analyzed using UPLC MS/MS system. It was found that the pyrethrolone moiety in pyrethrin II was derived from 12-oxo-phytodienoic acid (OPDA), iso -OPDA and cis -jasmone but not from methyl jasmonate and 3-oxo-2-(2′-[ Z ]-pentenyl)-cyclopentane-1-hexanoic acid. The results supported that the biosynthesis of the pyrethrolone moiety in pyrethrin II partially used part of the jasmonic acid biosynthetic pathway, but not whole.