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

Abstract

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. Graphical Abstract

Keywords

• Oxidative cleavage
• Austroeupatol
• NaIO4
• IBX
• Lactonization
• NMR