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In vivo transformations of artemisinic acid in Artemisia annua plants

Brown, G.D. and Sy, L.K. (2007) In vivo transformations of artemisinic acid in Artemisia annua plants. Tetrahedron, 63 (38). pp. 9548-9566. ISSN 0040-4020

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To link to this item DOI: 10.1016/j.tet.2007.06.062

Abstract/Summary

Artemisinic acid labeled with both C-13 and H-2 at the 15-position has been fed to intact plants of Artemisia annua via the cut stem, and its in vivo transformations studied by 1D- and 2D-NMR spectroscopy. Seven labeled metabolites have been isolated, all of which are known as natural products from this species. The transformations of artemisinic acid-as observed both for a group of plants, which was kept alive by hydroponic administration of water and for a group, which was allowed to die by desiccation-closely paralleled those, which have been recently described for its 11,13-dihydro analog, dihydroartemisinic acid. It seems likely therefore that similar mechanisms, involving spontaneous autoxidation of the Delta(4,5) double bond in both artemisinic acid and dihydroartemisinic acid and subsequent rearrangements of the resultant allylic hydroperoxides, may be involved in the biological transformations, which are undergone by both compounds. All of the sesquiterpene metabolites, which were obtained from in vivo transformations of artemisinic acid retained their unsaturation at the 11,13-position, and there was no evidence for conversion into any 11,13-dihydro metabolite, including artemisinin, the antimalarial drug, which is produced by A. annua. This observation led to the proposal of a unified biosynthetic scheme, which accounts for the biogenesis of many of the amorphane and cadinane sesquiterpenes that have been isolated as natural products from A. annua. In this scheme, there is a bifurcation in the biosynthetic pathway starting from amorpha-4,11-diene leading to either artemisinic acid or dihydroartemisinic acid; these two committed precursors are then, respectively, the parents for the two large families of highly oxygenated 11,13-dehydro and 11,13-dihydro sesquiterpene metabolites, which are known from this species. (C) 2007 Elsevier Ltd. All rights reserved.

Item Type:Article
Refereed:Yes
Divisions:Faculty of Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:11063
Uncontrolled Keywords:terpenes and terpenoids, biogenesis, autoxidation, NMR, EPI-DEOXYARTEANNUIN-B, DIHYDROARTEMISINIC ACID, ARTEANNUIN-B, AMORPHA-4,11-DIENE SYNTHASE, SPONTANEOUS AUTOXIDATION, SESQUITERPENE, LACTONE, BIOSYNTHESIS, ANTIMALARIAL, IDENTIFICATION, TERPENOIDS

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