Natural Products and Bioprospecting    2022, Vol. 12 Issue (3) : 20-20     DOI: 10.1007/s13659-022-00343-2
SHORT COMMUNICATION |
Preparation of a ε-caprolactonic diterpenoid derivate by unexpected oxidative cleavage/lactonization of 2-oxoaustroeupatol
Pablo A. Chacón-Morales1, Juan M. Amaro-Luis1, Luis Beltrán Rojas Fermín2, Rémi Jacquet3, Denis Deffieux3, Laurent Pouységu3, Stéphane Quideau3
1 Natural Products Laboratory, Department of Chemistry, Faculty of Science, University of Los Andes, Mérida, 5101, Venezuela;
2 Research Institute, Faculty of Pharmacy and Bioanalysis, University of Los Andes, Mérida, 5101, Venezuela;
3 ISM (CNRS-UMR 5255), Univ. Bordeaux, 351 cours de la Libération, 33405, Talence Cedex, France
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Abstract  From aerial parts of Austroeupatorium inulifolium was isolated the ent-nor-furano triol labdane austroeupatol 1. The compound 1 was treated with IBX showing an unexpected selectivity at the potentially oxidizable sites of the substrate yielding the 2-oxoaustroeupatol (2) and 2,19-dioxoaustroeupatol (3). The treatment of 2 with sodium periodate yields a heterocyclic derivative (ε-caprolactone derivate 4) formed by oxidative cleavage and unexpected intramolecular attack of the hydroxymethylene (C-19) oxygen to the ketonic carbon (C-2). A plausible mechanistic pathway for the obtention of compound 4 is proposed.
Keywords Oxidative cleavage      Austroeupatol      NaIO4      IBX      Lactonization      NMR     
Fund:This work was financially supported by the National Fund of Science, Technology and Innovation (FONACIT) (Grant N° 201300288) within the framework of the project PCP France-Venezuela and by the CDCHTA-ULA (Grant N° C-1935-15-08-ED). Thank are due to Eng. Juan Carmona Arzola, Department of Pharmacognosy and Organic Medicaments, Faculty of Pharmacy and Bioanalysis, University of Los Andes (ULA) for identification of plant material.
Corresponding Authors: Pablo A. Chacón-Morales,E-mail:pablochacon1@gmail.com     E-mail: pablochacon1@gmail.com
Issue Date: 24 June 2022
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Pablo A. Chacón-Morales
Juan M. Amaro-Luis
Luis Beltrán Rojas Fermín
Rémi Jacquet
Denis Deffieux
Laurent Pouységu
Stéphane Quideau
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Pablo A. Chacón-Morales,Juan M. Amaro-Luis,Luis Beltrán Rojas Fermín, et al. Preparation of a ε-caprolactonic diterpenoid derivate by unexpected oxidative cleavage/lactonization of 2-oxoaustroeupatol[J]. Natural Products and Bioprospecting, 2022, 12(3): 20-20.
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http://npb.kib.ac.cn/EN/10.1007/s13659-022-00343-2     OR     http://npb.kib.ac.cn/EN/Y2022/V12/I3/20
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