Biosynthesis of artemisia ketone in higher plants

Abstract

MVA-[2-14C], IPP-[4-14C] and DMAPP-[4-14C] were incorporated (optimum 0.04%–0.8 %) into artemisia ketone by Artemisia annua in a position-specific manner so that the C-5 moiety not containing the carbonyl group was preferentially (87–95 %) labelled. IPP and DMAPP, but not MVA, were similarly utilised in Santolina chamaecyparissus. Feeding of geraniol-[2-14C] to A.annua resulted in artemisia ketone being labelled in a position indicating extensive degradation of the precursor. 14C-labelled cis and trans-chrysanthemyl alcohols and chrysanthemates or DMVC were negligibly (< 5 × 10−4 %) incorporated into artemisia ketone in both species over a range of feeding conditions. (+)-trans-Chrysanthemyl alcohol-[Me14C] was an effective (ca 2 % incorporation) precursor of the terpenoid part of pyrethrins I and II in flowers of Chrysanthemum cinerariaefolium but 14C-labelled artemisyl alcohol (3, 3, 6-trimethylheptan-1, 5-dien-4-ol) or (±)-cis-chrysanthemyl alcohol were not detectably incorporated. Although some of the negligible incorporations are probably attributable to compartmentation effects preventing access of precursors to biosynthetic sites, the experiments indicate some limitation of the previously proposed pathways of biogenesis of artemisia ketone and related irregular monoterpenes.