Configurations and Sensory Properties of the Stereoisomers of 2,6-Dimethyl-4-propyl-1,3-oxathiane and 2,4-Dimethyl-6-propyl-1,3-oxathiane.

The heterocyclic compounds 2,6-dimethyl-4-propyl-1,3-oxathiane 1 and 2,4-dimethyl-6-propyl-1,3-oxathiane 2 were obtained by condensing 4-mercapto-2-heptanol and 2-mercapto-4-heptanol, respectively, with acetaldehyde. For both, separation of the eight stereoisomers was achieved via capillary gas chromatography using heptakis(diethyl-tert-butyldimethylsilyl)-ß-cyclodextrin as the chiral stationary phase. Their configurations were assigned by combinations of enzyme-catalyzed kinetic resolutions, HPLC separations, and assessments of NMR data. The odor thresholds and odor qualities of the stereoisomers were determined by capillary gas chromatography/olfactometry. The odor thresholds of the stereoisomers of 2 were generally higher than those of 1. For both oxathianes, the stereoisomers in which all substituents are in equatorial positions showed the highest odor thresholds. Most of the stereoisomers of 1 exhibited pleasant flowery, fruity, or sweet nuances; the stereoisomers of 2 were mainly characterized by descriptors, such as broth, mushroom, or pungent. The data demonstrate the impact of the positions of substituents and their spatial orientations on the sensory properties of 1,3-oxathianes.

Analytical and Sensory Characterization of the Stereoisomers of 3-Mercaptocycloalkanones and 3-Mercaptocycloalkanols.

3-Mercaptocycloalkanones and 3-mercaptocycloalkanols (chain lengths C5-C7) were obtained by addition of thioacetic acid to the respective 2-cycloalken-1-ones and subsequent enzyme-mediated hydrolysis and reduction with LiAlH4, respectively. The stereoisomers were separated via capillary gas chromatography using chiral stationary phases. Their configurations were determined based on 1H NMR data and enzyme-catalyzed kinetic resolutions. Odor thresholds and odor qualities were assessed by capillary gas chromatography/olfactometry. Compared to the analogous acyclic 4-mercapto-2-alkanones and 4-mercapto-2-alkanols, the cyclic polyfunctional thiols lacked fruity, tropical notes; the perceived odor properties ranged from cooked, roasted vegetables and meat types to onion-related notes. The odor thresholds of the enantiomers of the 3-mercaptocycloalkanones were mainly impacted by their ring size rather than their configuration. For the 3-mercaptocycloalkanols, the (S)-configuration at the stereogenic center bearing the thiol group and the relative configuration of the second asymmetric center with the hydroxyl group were of importance for low odor thresholds.

Absolute Configurations and Sensory Properties of the Stereoisomers of a Homologous Series (C6-C10) of 2-Mercapto-4-alkanols.

A homologous series (C6-C10) of 2-mercapto-4-alkanols was obtained by the addition of thioacetic acid to the respective alkenones and subsequent reduction with LiAlH4. Gas chromatographic separation of the stereoisomers was achieved using chiral stationary phases. Their absolute configurations were assigned by the correlation of 1H NMR data and enzyme-catalyzed kinetic resolutions. Odor thresholds and odor qualities were determined by capillary gas chromatography/olfactometry. Compared to the odor qualities reported for the isomeric 4-mercapto-2-alkanols, the homologous series of 2-mercapto-4-alkanols lacked fruity, tropical notes. There was no consistent correlation between the configurations and the odor qualities. However, the observed odor thresholds indicated the importance of the configuration of the asymmetric center bearing the hydroxyl group and the alkyl substituent. The length of this alkyl chain is a main driver for the odor properties, ranging from pungent, vegetable to earthy, mushroom notes.

Determination of the Absolute Configurations and Sensory Properties of the Enantiomers of a Homologous Series (C6-C10) of 2-Mercapto-4-alkanones.

The enantiomers of a homologous series (C6-C10) of 2-mercapto-4-alkanones were obtained by lipase-catalyzed kinetic resolution of the corresponding racemic 2-acetylthio-4-alkanones. Their configurations were assigned via vibrational circular dichroism and 1H NMR anisotropy based methods. Odor thresholds and odor qualities were determined by capillary gas chromatography-olfactometry using chiral stationary phases. There were minima of the odor thresholds for the chain lengths C7 and C8. Except for chain length C8, the enantiomers of the other homologues showed similar odor thresholds. The odor qualities ranged from pungent (C5) to mushroom (C9 and C10) and were similar to those known for the corresponding 1-alken-3-ones with one less C atom. In contrast to their positional isomers (4-mercapto-2-alkanones), the investigated 2-mercapto-4-alkanones do not meet the requirements of a "tropical olfactophore" (i.e., compounds possessing a 1,3-oxygen-sulfur functionality and specific arrangements of the substituents).