The enantiomeric contents of 2-pentanol of Baijiu were analyzed by liquid-liquid extraction (LLE) coupled with gas chromatography-mass spectrometry (GC-MS) using β-cyclodextrin as a chiral stationary phase. In this study, the average enantiomeric ratios R:S were 72:28, 64:36, and 94:6 in soy sauce aroma-type Baijiu (SSB), strong aroma-type Baijiu (STB), and light aroma-type Baijiu (LTB), respectively, and only (R)- configuration was found in rice aroma-type Baijiu (RTB). The highest enantiomeric concentration of 2-pentanol was found in STB. (R)-2-pentanol dominated in 48 Baijiu studied, and the concentration of (R)-2-pentanol was higher than that of the (S)-configuration. The results showed that the enantiomers of 2-pentanol were discrepant in different aroma types of Baijiu, and it may be the result of differences in raw materials, environment, and production processes. The 2-pentanol enantiomers had different odor characteristics, with different olfactory thresholds in pure water and 46% ethanol solutions by sensory analysis. (R)-2-pentanol was described as paint, rubber, grease, while the (S)-form had mint, plastic, and pungent notes. The olfactory thresholds of (R)- and (S)-form were 163.30 mg/L and 78.58 mg/L in 46% ethanol and 12.62 mg/L and 3.03 mg/L in pure water, respectively. The different enantiomeric distribution and aroma characteristics of the 2-pentanol enantiomers in Baijiu could be a potential marker for determining adulteration.

Retronasal aroma strongly influences the flavor quality of low-alcohol Jiangxiangxing Baijiu. This study investigated the retronasal aroma differences between high- and low-alcohol samples (Sample-High and Sample-Low). Dynamic sensory evaluation revealed roasted, grain, floral and fruity, hay, and caramel notes were more pronounced in Sample-High, whereas Sample-Low exhibited stronger fatty and smoky notes, indicating insufficient retronasal aroma richness in Sample-Low. Analysis of 67 compounds showed no significant concentration differences, yet their retronasal olfactory thresholds varied markedly between alcoholic systems (ratio 1.04–4.75), leading to higher dose-over-threshold (DoT) values for several compounds in Sample-Low. Further analysis of the DoT distribution intervals showed Sample-High presented a more balanced distribution, whereas Sample-Low was strongly driven by several high-contribution compounds, which reduced the relative contributions of others. This unbalanced distribution may underlie the lower retronasal aroma richness observed in Sample-Low. These findings provide a new perspective for understanding retronasal aroma in low-alcohol Jiangxiangxing Baijiu.