Enantioselective Analysis of Free and Glycosidically Bound Monoterpene Polyols in <i>Vitis vinifera</i> L. Cvs. Morio Muscat and Muscat Ottonel:  Evidence for an Oxidative Monoterpene Metabolism in Grapes

Abstract

The enantiomeric ratios of various free and glycosidically bound monoterpene polyols in musts of the aromatic grapes Vitis vinifera L. cvs. Morio Muscat and Muscat Ottonel were determined by means of enantioselective multidimensional gas chromatography−mass spectrometry. Reference compounds of defined stereochemistry were synthesized and permitted the unequivocal determination of the elution order of the target compounds on chiral columns with modified cyclodextrins as stationary phases. It could be shown for the first time that the linalool-derived polyol 3,7-dimethylocta-1,7-dien-3,6-diol occurs predominately as the (3 S,6 S )-configured stereoisomer, providing evidence that this compound is generated by an enzymatic process in grape berries. The involvement of a cytochrome P450 monooxygenase in the oxidative metabolism of monoterpenes in grapes is dicussed. Keywords: Vitis vinifera L.; monoterpene polyols; oxidative metabolism; biosynthesis; enantioselective multidimensional gas chromatography−mass spectrometry (enantio-MDGC/MS)