Enantiodifferentiation of whisky and cognac lactones using gas chromatography with different cyclodextrin chiral stationary phases

• Published in: Journal of Chromatography A 2017-09, Vol.1516, p.135-141
• Main Authors: Schmarr, Hans-Georg, Mathes, Maximilian, Wall, Kristina, Metzner, Frank, Fraefel, Marius
• Format: Article
• Language: English
• Subjects: Baker’s yeast reduction; Chiral stationary phase; Cognac lactone; Enantioseparation; Gas chromatography; Whisky lactone
• ISSN: 0021-9673
• DOI: 10.1016/j.chroma.2017.08.010

•Direct gas chromatographic enantioseparation of whisky and cognac lactone.•Determination of elution orders on various cyclodextrin-based stationary phases.•Enantioselective baker’s yeast reduction of ethyl 3-methyl-4-oxononanoate.•Determination of linear retention indices on achiral stationary phases.•Positive chemical ionization mass spectra of whisky and cognac lactone. The chiral lactone 5-butyl-4-methyloxolan-2-one or 5-butyl-4-methyldihydro-2(3H)-furanone, often named whisky lactone, is found in oak wood, then contributing to the appreciated flavor of beverages stored in such wooden barrels. Its next higher homologue is named cognac lactone (5-pentyl-4-methyloxolan-2-one or 5-pentyl-4-methyldihydro-2(3H)-furanone), however is much less known, probably due to its minor concentration level. In order to study the direct enantioseparation of both lactones by gas chromatography on chiral stationary phases, individual enantiomers, particularly for cognac lactone were made available. This was achieved by baker’s yeast reduction of synthesized ethyl 3-methyl-4-oxononanoate or, after hydrolysis, of the corresponding 4-ketoacid, that gave access to individual enantiomers of cognac lactone. Good enantioseparation was achieved for both whisky and cognac lactone with high values for the chiral resolution with 6-O-tert. butyl dimethylsilyl-2,3-dialkylated or 6-O-tert. butyl dimethylsilyl-2,3-diacylated cyclodextrin derivatives as chiral selectors. The influence of the nature and position of derivatization of the cyclodextrin moiety revealed a strong impact on the chiral recognition mechanism, as the investigated alkylated derivatives heptakis-(2,6-di-O-iso-pentyl-3-O-allyl)-β-cyclodextrin and octakis-(2,3-di-O-pentyl-6-O-methyl)-γ-cyclodextrin did not provide any or only minor chiral selectivity for the two lactones.