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During the past 20 years, interest in the involvement of varietal thiols in the aroma of young wines has grown considerably. Most data in the literature dealing with these thiols in wine has focused on 4-mercapto-4-methylpentan-2-one, 3-mercaptohexyl acetate and 3-mercaptohexan-1-ol and demonstrate the central role of the different branches of chemistry in understanding the biotechnological processes responsible for thiol release. This review describes and discusses the chemical strategies used to synthesize volatile thiols and their precursors as well as their final use in order to: (1) elucidate the structure of the precursors, their role and the mechanism of cleavage; (2) determine the sensory contribution of volatile thiols in wine; and (3) develop accurate quantification methods. Copyright © 2012 John Wiley & Sons, Ltd.