Two additional 1,9-diarylnonanoid 3-glucosides from Erica cinerea among which an unusual α-dione in conformational equilibrium

Continuation of the phytochemical analysis of Erica cinerea fresh aerial parts resulted in the isolation of two new compounds with a very close chromatographic behavior. On the basis of spectroscopic evidence (UV, MS and NMR), the structures were established as (−)-(3S,6E)-1,9-bis(p-hydroxyphenyl)-3-hydroxynon-6-en-5-one 3-O-β-d-glucoside named 6,7-anhydroericaone 3-O-β-d-glucoside and (−)-(3S)-1,9-bis(p-hydroxyphenyl)-3-hydroxynonan-5,6-dione 3-O-β-d-glucoside named α-ericadione 3-O-β-d-glucoside. Unanticipated by its α-alkadione type structure —a very unusual feature in the plant kingdom— the latter metabolite was found as a mixture of the minor s-cis and the major s-trans conformers. Moreover, the GC–MS analysis of the aglycone moieties of such glucosides, pointed out the permanent absence of the molecular ion and the constant hydroxybenzylium base peak, as well as the conversion of the α-dione into the major α-keto-enol tautomer.