Preparation of a ε-caprolactonic diterpenoid derivate by unexpected oxidative cleavage/lactonization of 2-oxoaustroeupatol

doi:10.1007/s13659-022-00343-2

应用天然产物 ›› 2022, Vol. 12 ›› Issue (3): 20-20.DOI: 10.1007/s13659-022-00343-2

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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

收稿日期:2022-01-25 出版日期:2022-06-24 发布日期:2022-06-24
通讯作者: Pablo A. Chacón-Morales,E-mail:pablochacon1@gmail.com
基金资助:
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.

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

Received:2022-01-25 Online:2022-06-24 Published:2022-06-24
Contact: Pablo A. Chacón-Morales,E-mail:pablochacon1@gmail.com
Supported by:
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.

摘要/Abstract

摘要： 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.

关键词: Oxidative cleavage, Austroeupatol, NaIO₄, IBX, Lactonization, NMR

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.

Key words: Oxidative cleavage, Austroeupatol, NaIO₄, IBX, Lactonization, NMR

Pablo A. Chacón-Morales, Juan M. Amaro-Luis, Luis Beltrán Rojas Fermín, Rémi Jacquet, Denis Deffieux, Laurent Pouységu, Stéphane Quideau. Preparation of a ε-caprolactonic diterpenoid derivate by unexpected oxidative cleavage/lactonization of 2-oxoaustroeupatol[J]. 应用天然产物, 2022, 12(3): 20-20.

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Preparation of a ε-caprolactonic diterpenoid derivate by unexpected oxidative cleavage/lactonization of 2-oxoaustroeupatol

Preparation of a ε-caprolactonic diterpenoid derivate by unexpected oxidative cleavage/lactonization of 2-oxoaustroeupatol

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