Biosynthesis of anthecotuloide, an irregular sesquiterpene lactone from Anthemis cotula L. (Asteraceae) via a non-farnesyl diphosphate route.
Retrobiosynthetic analysis of the allergenic sesquiterpene lactone, anthecotuloide, suggested that this natural product could be formed either by head to head condensation of geranyl diphosphate with dimethylallyl diphosphate, or from farnesyl diphosphate (FPP), the accepted regular sesquiterpene precursor via the rearrangement of a germacranolide precursor. Isotopic labelling of anthecotuloide has now been achieved by feeding [1-(13)C]-glucose, [U-13C6]-glucose and [6,6-(2)H2]-glucose to aseptically grown plantlets of Anthemis cotula(family Asteraceae). Analysis of labelling patterns and absolute 13C abundances using quantitative 13C NMR spectroscopy showed that the isoprene building blocks of this sesquiterpene are formed exclusively via the MEP terpene biosynthetic pathway. This was supported by results from an experiment using [U-13C6]-glucose. A deuterium labelling experiment using [6,6-(2)H2]-glucose supported the original proposal and showed that anthecotuloide is formed from a non FPP precursor. Isotope ratio mass spectrometry suggested that there were two pathways for sesquiterpene biosynthesis in A. cotula.
van Klink
John
J
Plant Extracts Research Unit, New Zealand Institute for Crop & Food Research Limited, Department of Chemistry, University of Otago, P.O. Box 56, Dunedin, New Zealand. vanklinl@crop.cri.nz
Becker
Hans
H
Andersson
Susannah
S
Boland
Wilhelm
W
D031166:Anthemis / Q000737:chemistry* / Q000378:metabolism*; D002247:Carbon Isotopes; D003903:Deuterium; D004896:Erythritol / Q000031:analogs & derivatives / Q000378:metabolism; D005947:Glucose / Q000031:analogs & derivatives / Q000378:metabolism; D007783:Lactones / Q000737:chemistry / Q000378:metabolism*; D009682:Magnetic Resonance Spectroscopy; D011106:Polyisoprenyl Phosphates; D012717:Sesquiterpenes / Q000737:chemistry / Q000378:metabolism*; D013729:Terpenes / Q000378:metabolism
D002247:Carbon Isotopes; D007783:Lactones; D011106:Polyisoprenyl Phosphates; D012717:Sesquiterpenes; D013729:Terpenes; C004808:farnesyl pyrophosphate; D003903:Deuterium; D005947:Glucose; D004896:Erythritol