Distribution and organoleptic impact of ethyl 2-hydroxy-4-methylpentanoate enantiomers in wine

The enantiomers of ethyl 2-hydroxy-4-methylpentanoate (ethyl dl-leucate) were assayed in several wines using chiral gas chromatography (γ-cyclodextrin). Analyses of 55 commercial wines from various vintages and origins revealed different distributions. Generally, white wines presented only the R form, whereas red wines contained both enantiomers, in various ratios according to aging. The highest levels of the S form were found in the oldest samples. The R/S average enantiomeric ratio of this compound in red wine was approximately 95:5 with an average total concentration of ∼400 μg/L. The olfactory threshold of R-ethyl 2-hydroxy-4-methylpentanoate (126 μg/L) in hydroalcoholic solution was almost twice that of the S form (55 μg/L). The olfactory threshold of a mixture of R- and S-ethyl 2-hydroxy-4-ethylpentanoate (95:5, m/m) in hydroalcoholic solution was 51 μg/L, suggesting that both enantiomeric forms contribute to perception of this compound in wine, resulting in a synergistic effect. Both enantiomers have quite similar aromatic nuances. Sensory analysis was employed to demonstrate a synergistic effect of this ethyl ester on the perception of fruity aromas in wine: in hydroalcoholic solution supplemented with R- or S-ethyl 2-hydroxy-4-methylpentanoate or a mixture of the R and S forms (95:5, m/m) at their average concentrations in red wines, fruity character was perceived at concentrations 2.2, 4.5, and 2.5 times lower, respectively, than in hydroalcoholic solution alone. Sensory profiles of aromatic reconstitutions, using HPLC fruity fractions, highlighted the contribution of this compound to blackberry fruit and fresh fruit descriptors.