Wine lactone

A very important lactone in wines is the so-called wine lactone," 3a,4,5,7a-tetrahydro-3,6-dimethyl-2(3H)-benzofuranone 5, which exists in four enantiomeric pairs. This compound was first identified and isolated from the urine of Koala bears (75TL1885, 97JAFC3027), from their diet of the leaves of the Eucalyptus punctata tree. And this shows that the wine lactone belongs to monoterpenoid flavoring ingredients, which have been converted into oxygenated forms. 

Whereas the glucose ester 9 has been identified for the first time as a natural wine constituent, glycoconjugates of its reduced form, i.e. of the monoterpene diol 11, are known Riesling wine constituents (2). Under acidic conditions, diol 11 was partially converted into the bicyclic ether 12, the so-called dillether (2). In analogy to the formation of ether 12 from terpene diol 11, a likely formation of lactone 10 from acid 9A could be be expected (cf. Fig. 5). This so-called wine-lactone 10, first identified as an essential oil metabolite in the Koala (55), has recently been established by Guth (34) as a major aroma contributor in two white wine varieties. The 35,3a5,7aR-configured isomer of 10, which has been identified in wine, is reported to possess an unusual low flavor threshold of 0.01-0.04 pg/L of air and a sweet, coconut-like aroma (55). 

Figure 5. Postulated formation of wine-lactone 10 from monoterpenoid acid 9A in analogy to dillether 12 formation from the structurally related chol 11.

Recently, AEDA and SHA-0 yielded 41 and 45 odor active compounds for Scheurebe and Gewurztraminer wines, respectively (P). Ethyl 2-methylbutyrate, ethyl isobutyrate, 2-phenylethanol, 3-methylbutanol, 3-hydroxy-4,5-dimethyl-2(5H)-furanone, 3-ethylphenol and one unknown compound, named wine lactone, showed high flavor dilution (FD)- factors (Table I) in Gewurztraminer and Scheurebe wines. 4-Mercapto-4-methylpentan-2-one belongs to the most potent odorants only in the variety Scheurebe whereas cis-rose oxide was perceived only in Gewurztraminer (Table I). 4-Mercapto-4-methylpentan-2-one was identified for the first time in Sauvignon blanc wines (JO). The unknown compound with coconut, woody and sweet odor quality, which has not yet been detected in wine or a food, was identified as 3a,4,5,7a-tetrahydro-3,6-dimethylbenzofuran-2(3H)-one (wine lactone) (JJ). 

Because of the three asymmetric centers in the molecule there exist eight different stereoisomers. To identify the stereochemistry of wine lactone syntheses for the enantiomers were developed. On the basis of enantioselective gas chromatography the stereochemistry of wine lactone was in agreement with the 3S,3aS,7aR-enantiomer (72) for this stereoisomer a low odor threshold was determined (0.00002 ng/L air) ... 

Wine lactone Ethyl isobutyrate Ethyl 2-methylbutyrate... 

A suitable tool for the quantitation of trace compounds in foods is a stable isotope dilution assay (IVA) 16, 17). Allen et al. (18) used the IVA for the quantification of two methoxypyrazines in red wines, Guth (77) quantified wine lactone in various red and white wines and Aubry et al. (7P) used the technique for the determination of four esters (ethyl dihydrocinnamate, ethyl cinnamate, methyl anthranilate and ethyl anthranilate) in Pinot Noir wines. 

To estimate the sensory contribution of the 42 odorants to the overall flavor of the wine samples, their OAV s were calculated (Table II). To take into account the influence of ethanol, the odor threshold values of wine odorants were determined in a mixture of water/ethanol (9+1, w/w) and were used to calculate the OAV s for each compound. According to the results in Table A, 4-mercapto-4-methylpentan-2-one, ethyl octanoate, ethyl hexanoate, 3-methylbutyl acetate, ethyl isobutyrate, (E)-fi-damascenone, linalool, cis rose oxide and wine lactone showed the highest OAV s in the Scheurebe wine. With exception of 4-mercapto-4-methylpentan-2-one the above mentioned odorants also showed the highest OAV s in Gewurztraminer wine. Differences in the OAV s of ethyl octanoate, ethyl hexanoate, 3-methylbutyl acetate and ethyl isobutyrate between the two varieties are probably caused by differences in the maturity of the fruit at harvest and/or by the fermentation process. 

Figure 2. Concentrations of cis-rose oxide, linalool, (E)-li-damascenone and wine lactone in different stages of wine making 1 = after pressing of grapes, 2 = after yeast fermentation, 3 = after malolactic fermentation, 4 = after maturing in high-grade steel...

Figure 5.1a (Continued) octadiene-3,6-diol) (11) hydroxycitronellol (3,7-di methyloctane-l,7-diol) (12) 8-hydroxydihydrolinalool (2,6-dimethyl-7-octene-l,6-diol) (13) 7-hydroxygeraniol (E-3,6-dimethyl-2-octene-l,7-diol) (14) 7-hydro-xynerol (Z-3,6-dimethyl-2-octene-l, 7-diol) (15) cis and trans 8-hydroxy linalool (E- and Z-2,6-dimethyl-2,7-octadiene-l,6-diol) (16) p-menthenediol I (p-menth-l-ene-7,8-diol) (17) E-geranic acid (3,7-dimethyl-2,6-octadienoic acid) (18) E-2,6-dimethyl-6-hydroxyocta-2,7-dienoic acid (19) E- and Z-sobrerol or p-menthenediol II (p-menth-l-ene-6,8-diol) (20) cis and trans rose oxide (21) nerol oxide (22) 2-exo-hydroxy-1,8-cineol (23) 1,8-cineol (24) wine lactone (25) cis and trans 1,8-terpin (26) triol (2,6-dimethyloctane-2,3,6-triol) (27) hotrienol [(5E)-3,5-dimethylocta-l,5,7-trien-3-ol] (28) myrcenol (2-methyl-6-methylene-7-octen-2-ol)...

Activated methylene compounds such as dimethyl malonate have found substantial utility in palladium catalyzed allylic substitution reactions. Accordingly, the Krapcho decarboxylation is often used in conjunction with these reactions. As an example, the first total synthesis of enantiomerically pure (-)-wine lactone has utilized the sequence of reactions.27 First, the allylic substitution reaction of 2-cyclohexen-l-yl acetate (49) with alkali sodium dimethylmalonate yielded 51 with high enantioselectivity, as a result of the use of chiral phosphine ligand 50. The malonate was then subjected to Krapcho decarbomethoxylation using NaCl, H2O, and DMSO at 160 °C to yield 52. This reaction has been used similarly following the allylic substitution reaction with other malonate derivatives.28-30... 

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