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Article: In vivo transformations of dihydroartemisinic acid in Artemisia annua plants

TitleIn vivo transformations of dihydroartemisinic acid in Artemisia annua plants
Authors
KeywordsAutoxidation
Biogenesis
Nmr
Terpenes And Terpenoids
Issue Date2004
PublisherPergamon. The Journal's web site is located at http://www.elsevier.com/locate/tet
Citation
Tetrahedron, 2004, v. 60 n. 5, p. 1139-1159 How to Cite?
Abstract[15-13C2H3]-dihydroartemisinic acid (2a) and [15-C2H3]-dihydroartemisinic acid (2b) have been fed via the root to intact Artemisia annua plants and their transformations studied in vivo by one-dimensional 2H NMR spectroscopy and two-dimensional 13C-2H correlation NMR spectroscopy (13C- 2H COSY). Labelled dihydroartemisinic acid was transformed into 16 12-carboxy-amorphane and cadinane sesquiterpenes within a few days in the aerial parts of A. annua, although transformations in the root were much slower and more limited. Fifteen of these 16 metabolites have been reported previously as natural products from A. annua. Evidence is presented that the first step in the transformation of dihydroartemisinic acid in vivo is the formation of allylic hydroperoxides by the reaction of molecular oxygen with the Δ 4,5-double bond in this compound. The origin of all 16 secondary metabolites might then be explained by the known further reactions of such hydroperoxides. The qualitative pattern for the transformations of dihydroartemisinic acid in vivo was essentially unaltered when a comparison was made between plants, which had been kept alive and plants which were allowed to die after feeding of the labelled precursor. This, coupled with the observation that the pattern of transformations of 2 in vivo demonstrated very close parallels with the spontaneous autoxidation chemistry for 2, which we have recently demonstrated in vitro, has lead us to conclude that the main 'metabolic route' for dihydroartemisinic acid in A. annua involves its spontaneous autoxidation and the subsequent spontaneous reactions of allylic hydroperoxides which are derived from 2. There may be no need to invoke the participation of enzymes in any of the later biogenetic steps leading to all 16 of the labelled 11,13-dihydro-amorphane sesquiterpenes which are found in A. annua as natural products. © 2003 Elsevier Ltd. All rights reserved.
Persistent Identifierhttp://hdl.handle.net/10722/167861
ISSN
2015 Impact Factor: 2.645
2015 SCImago Journal Rankings: 0.991
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorBrown, GDen_US
dc.contributor.authorSy, LKen_US
dc.date.accessioned2012-10-08T03:12:16Z-
dc.date.available2012-10-08T03:12:16Z-
dc.date.issued2004en_US
dc.identifier.citationTetrahedron, 2004, v. 60 n. 5, p. 1139-1159en_US
dc.identifier.issn0040-4020en_US
dc.identifier.urihttp://hdl.handle.net/10722/167861-
dc.description.abstract[15-13C2H3]-dihydroartemisinic acid (2a) and [15-C2H3]-dihydroartemisinic acid (2b) have been fed via the root to intact Artemisia annua plants and their transformations studied in vivo by one-dimensional 2H NMR spectroscopy and two-dimensional 13C-2H correlation NMR spectroscopy (13C- 2H COSY). Labelled dihydroartemisinic acid was transformed into 16 12-carboxy-amorphane and cadinane sesquiterpenes within a few days in the aerial parts of A. annua, although transformations in the root were much slower and more limited. Fifteen of these 16 metabolites have been reported previously as natural products from A. annua. Evidence is presented that the first step in the transformation of dihydroartemisinic acid in vivo is the formation of allylic hydroperoxides by the reaction of molecular oxygen with the Δ 4,5-double bond in this compound. The origin of all 16 secondary metabolites might then be explained by the known further reactions of such hydroperoxides. The qualitative pattern for the transformations of dihydroartemisinic acid in vivo was essentially unaltered when a comparison was made between plants, which had been kept alive and plants which were allowed to die after feeding of the labelled precursor. This, coupled with the observation that the pattern of transformations of 2 in vivo demonstrated very close parallels with the spontaneous autoxidation chemistry for 2, which we have recently demonstrated in vitro, has lead us to conclude that the main 'metabolic route' for dihydroartemisinic acid in A. annua involves its spontaneous autoxidation and the subsequent spontaneous reactions of allylic hydroperoxides which are derived from 2. There may be no need to invoke the participation of enzymes in any of the later biogenetic steps leading to all 16 of the labelled 11,13-dihydro-amorphane sesquiterpenes which are found in A. annua as natural products. © 2003 Elsevier Ltd. All rights reserved.en_US
dc.languageengen_US
dc.publisherPergamon. The Journal's web site is located at http://www.elsevier.com/locate/teten_US
dc.relation.ispartofTetrahedronen_US
dc.subjectAutoxidationen_US
dc.subjectBiogenesisen_US
dc.subjectNmren_US
dc.subjectTerpenes And Terpenoidsen_US
dc.titleIn vivo transformations of dihydroartemisinic acid in Artemisia annua plantsen_US
dc.typeArticleen_US
dc.identifier.emailSy, LK:sylk@hkucc.hku.hken_US
dc.identifier.authoritySy, LK=rp00784en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1016/j.tet.2003.11.070en_US
dc.identifier.scopuseid_2-s2.0-0346964232en_US
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0346964232&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume60en_US
dc.identifier.issue5en_US
dc.identifier.spage1139en_US
dc.identifier.epage1159en_US
dc.identifier.isiWOS:000188536800012-
dc.publisher.placeUnited Kingdomen_US
dc.identifier.scopusauthoridBrown, GD=7406468149en_US
dc.identifier.scopusauthoridSy, LK=35874602700en_US

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