Synthesis, structure elucidation, and olfactometric analysis of lilac aldehyde and lilac alcohol stereoisomers.

Structure elucidation of the lilac aldehyde and lilac alcohol stereoisomers was ascertained by (1)H nuclear magnetic resonance (NMR) spectroscopy, including intramolecular nuclear Overhauser effects of the separated diastereoisomers and anisotropic effects of the diastereomeric 2-phenylpropionyl ester, and (1)H, (1)H COSY NMR spectroscopy of synthesized (5'R)-configured stereoisomers, synthesized from (R)-linalool. Direct stereodifferentiation of the eight stereoisomers of lilac aldehyde and lilac alcohol, respectively, has been achieved, using enantioselective capillary GC. The elution order of the isomers was deduced from the chromatographic behavior of the (5'R)-configured diastereoisomers. Additionally, the odor thresholds of lilac aldehyde and lilac alcohol stereoisomers are reported.

Biogenetic studies in Syringa vulgaris L.: synthesis and bioconversion of deuterium-labeled precursors into lilac aldehydes and lilac alcohols.

Syringa vulgaris L. inflorescences were fed with aqueous solutions of regioselectively deuterated compounds assumed to be precursors of lilac aldehyde and lilac alcohol, respectively. Volatiles were extracted by stir bar sorptive extraction (SBSE) and analyzed using enantioselective multidimensional gas chromatography/mass spectrometry (enantio-MDGC/MS); deuterium-labeled lilac aldehydes and lilac alcohols were separated from unlabeled stereoisomers on a fused silica capillary column, coated with heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl)-beta-cyclodextrin (DIME-beta-CD) (30%) in SE 52 (70%), as the chiral stationary phase. Feeding experiments with [5,5-(2)H(2)]mevalonic acid lactone 22 and [5,5-(2)H(2)]deoxy-d-xylose 23 indicate that the novel mevalonate independent 1-deoxy-d-xylose 5-phosphate/2C-methyl-d-erythritol 4-phosphate pathway is the dominant metabolic route for biosynthesis in lilac flowers. Additionally, bioconversion of deuterium-labeled d(5)-(R/S)-linalool 3, d(6)-(R)-linalool 21, d(5)-(R/S)-8-hydroxylinalool 6, d(5)-(R/S)-8-oxolinalool 7, d(5)-lilac aldehydes 8-11 and d(5)-lilac alcohols 12-15 into lilac during in vivo feeding experiments was investigated and the metabolic pathway is discussed. Incubation of petals with an aqueous solution of deuterated d(5)-(R/S)-linalool 3 indicates an autonomic terpene biosynthesis of lilac flavor compounds in the flower petals of lilac.