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Published on: September 2, 2020
Acyloxyneryl esters in Doronicum austriacum subsp. giganteum essential oil: structure elucidation, synthesis, and
Milan Ž Dimitrijević1, Irena Lj Raca2, Niko S Radulović1
1Department of Chemistry, Faculty of Sciences and Mathematics, University of Niš, Višegradska 33, 18000, Niš, Serbia.
Abstract:
The essential oil of the underground parts of Doronicum austriacum subsp. giganteum (Griseb.) Stoj. & Stef. (Asteraceae) was studied here for the first time. Based GC-FID peak-area normalization, neryl isobutyrate (44.2%) and neryl 2-methylbutyrate (28.8%) were the two most abundant identified constituents. Targeted chromatographic fractionation guided by GC-MS revealed a series of oxygenated acyclic monoterpene diesters that proved difficult to identify by conventional means. By combining the synthesis of authentic reference compounds with high-field NMR spectroscopy (HSQC, HMBC, NOESY) and diagnostic 13C-1H coupling constants, nine previously undescribed natural products were identified, including 8- and 9-acyloxyneryl isobutyrates and the corresponding 2-methylbutyrate analogues. Systematic relationships between structure and linear retention indices on nonpolar and polar stationary phases provided transferable criteria for distinguishing C-8 vs C-9 oxygenation and neryl (Z) vs geranyl (E) geometry, and enabled estimation of chromatographic behavior for related, not-yet observed congeners. A re-evaluation of reported NMR patterns further suggests that a subset of literature "acyloxyneryl/geranyl" assignments may correspond to C-10-acylated isomers. Collectively, these findings expand the phytochemical space of acylated monoterpenes in Asteraceae roots and provide a validated spectral and retention-index reference framework for future studies of closely related metabolites.
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