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Surprising structural lability of a cysteine-S-conjugate precursor of 4-methyl-4-sulfanylpentan-2-one, a varietal aroma in wine of Vitis vinifera L. cv. Sauvignon blanc.
Chem Biodivers. 2008 May; 5(5):793-810.CB

Abstract

4-Methyl-4-sulfanylpentan-2-one (1; 4MSP) provides a characteristic aroma compound of wines made from Vitis vinifera L. cv. Sauvignon blanc. 4MSP has a strong box-tree odor with a very low perception threshold and is derived from the cysteinylated precursor S-(1,1-dimethyl-3-oxobutyl)cysteine (4; P-4MSP). P-4MSP is transformed into 4MSP during alcoholic fermentation and is an excellent marker of varietal aroma potential. An improved synthesis of P-4MSP as well as of its deuterium-labeled analogue [D(6)]-P-4MSP is described. Several analytical methods (NMR, IR, LSI-MS, GC/MS, ESI-MS(n)) were combined to elucidate spontaneous reversible structural changes of P-4MSP at different pH values. At low pH, P-4MSP has a linear keto form. The keto-enol tautomerism was observed at neutral pH. At pH 8, the formation of N-substituted intramolecular hemiaminal was characterized by ESI-MS and ESI-MS(n) experiments. The hemiaminal loses H(2)O at high pH to produce a cycloimine, which is easily opened by acid hydrolysis. The keto-enol tautomerism explained the incorporation of only six D-atoms during the preparation of the P-4MSP deuterated standard even if [D(10)]mesityl oxide was used. Derivatization conditions for GC/MS analysis strongly affected the ratio of the monosilylated intramolecular cyclic form and the disilylated linear form of P-4MSP. The structural changes of P-4MSP may have a considerable impact on the development of methods of measuring varietal aroma potential.

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Authors+Show Affiliations

Shinkaruk S
ENITA de Bordeaux, 1 cours du Général de Gaulle, CS 40201, F-33175 Gradignan Cedex, France. s-poix-shinkaruk@enitab.fr
Thibon C
No affiliation info available
Schmitter JM
No affiliation info available
Babin P
No affiliation info available
Tominaga T
No affiliation info available
Degueil M
No affiliation info available
Desbat B
No affiliation info available
Jussier C
No affiliation info available
Bennetau B
No affiliation info available
Dubourdieu D
No affiliation info available
Bennetau-Pelissero C
No affiliation info available

MeSH

CyclizationCysteineDatabases, FactualGas Chromatography-Mass SpectrometryMagnetic Resonance SpectroscopyMolecular StructurePentanonesSpectrophotometry, InfraredSulfhydryl CompoundsVitisWine

Pub Type(s)

Journal Article

Language

eng

PubMed ID

18493966

Citation

Shinkaruk, Svitlana, et al. "Surprising Structural Lability of a cysteine-S-conjugate Precursor of 4-methyl-4-sulfanylpentan-2-one, a Varietal Aroma in Wine of Vitis Vinifera L. Cv. Sauvignon Blanc." Chemistry & Biodiversity, vol. 5, no. 5, 2008, pp. 793-810.
Shinkaruk S, Thibon C, Schmitter JM, et al. Surprising structural lability of a cysteine-S-conjugate precursor of 4-methyl-4-sulfanylpentan-2-one, a varietal aroma in wine of Vitis vinifera L. cv. Sauvignon blanc. Chem Biodivers. 2008;5(5):793-810.
Shinkaruk, S., Thibon, C., Schmitter, J. M., Babin, P., Tominaga, T., Degueil, M., Desbat, B., Jussier, C., Bennetau, B., Dubourdieu, D., & Bennetau-Pelissero, C. (2008). Surprising structural lability of a cysteine-S-conjugate precursor of 4-methyl-4-sulfanylpentan-2-one, a varietal aroma in wine of Vitis vinifera L. cv. Sauvignon blanc. Chemistry & Biodiversity, 5(5), 793-810. https://doi.org/10.1002/cbdv.200890076
Shinkaruk S, et al. Surprising Structural Lability of a cysteine-S-conjugate Precursor of 4-methyl-4-sulfanylpentan-2-one, a Varietal Aroma in Wine of Vitis Vinifera L. Cv. Sauvignon Blanc. Chem Biodivers. 2008;5(5):793-810. PubMed PMID: 18493966.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Surprising structural lability of a cysteine-S-conjugate precursor of 4-methyl-4-sulfanylpentan-2-one, a varietal aroma in wine of Vitis vinifera L. cv. Sauvignon blanc. AU - Shinkaruk,Svitlana, AU - Thibon,Cécile, AU - Schmitter,Jean-Marie, AU - Babin,Pierre, AU - Tominaga,Takatoshi, AU - Degueil,Marie, AU - Desbat,Bernard, AU - Jussier,Christophe, AU - Bennetau,Bernard, AU - Dubourdieu,Denis, AU - Bennetau-Pelissero,Catherine, PY - 2008/5/22/pubmed PY - 2008/8/20/medline PY - 2008/5/22/entrez SP - 793 EP - 810 JF - Chemistry & biodiversity JO - Chem Biodivers VL - 5 IS - 5 N2 - 4-Methyl-4-sulfanylpentan-2-one (1; 4MSP) provides a characteristic aroma compound of wines made from Vitis vinifera L. cv. Sauvignon blanc. 4MSP has a strong box-tree odor with a very low perception threshold and is derived from the cysteinylated precursor S-(1,1-dimethyl-3-oxobutyl)cysteine (4; P-4MSP). P-4MSP is transformed into 4MSP during alcoholic fermentation and is an excellent marker of varietal aroma potential. An improved synthesis of P-4MSP as well as of its deuterium-labeled analogue [D(6)]-P-4MSP is described. Several analytical methods (NMR, IR, LSI-MS, GC/MS, ESI-MS(n)) were combined to elucidate spontaneous reversible structural changes of P-4MSP at different pH values. At low pH, P-4MSP has a linear keto form. The keto-enol tautomerism was observed at neutral pH. At pH 8, the formation of N-substituted intramolecular hemiaminal was characterized by ESI-MS and ESI-MS(n) experiments. The hemiaminal loses H(2)O at high pH to produce a cycloimine, which is easily opened by acid hydrolysis. The keto-enol tautomerism explained the incorporation of only six D-atoms during the preparation of the P-4MSP deuterated standard even if [D(10)]mesityl oxide was used. Derivatization conditions for GC/MS analysis strongly affected the ratio of the monosilylated intramolecular cyclic form and the disilylated linear form of P-4MSP. The structural changes of P-4MSP may have a considerable impact on the development of methods of measuring varietal aroma potential. SN - 1612-1880 UR - https://www.unboundmedicine.com/medline/citation/18493966/Surprising_structural_lability_of_a_cysteine_S_conjugate_precursor_of_4_methyl_4_sulfanylpentan_2_one_a_varietal_aroma_in_wine_of_Vitis_vinifera_L__cv__Sauvignon_blanc_ L2 - https://doi.org/10.1002/cbdv.200890076 DB - PRIME DP - Unbound Medicine ER -