Identification of intermediates involved in the biosynthetic pathway of 3-mercaptohexan-1-ol conjugates in yellow passion fruit (Passiflora edulis f. flavicarpa)

Yellow passion fruit is one of the most well-known tropical fruits and much of its success comes from its typical aroma. Key compounds in explaining yellow passion fruit scent are volatile thiols. These molecules are reported to be present in several fruits and originate from non-volatile precursors. Such free thiols are particularly appreciated in white wines and considerable efforts have been made to try to maximise their production and understand their biosynthesis. Two main precursors have been identified so far: S-glutathionylated and S-cysteinylated precursors, the latter originating in the breaking down of the glycyl and glutamyl moieties of the former. Improving knowledge about this pathway is currently one of the main challenges in the field of aroma chemistry. Only S-cysteinylated precursors have been reported in the literature for yellow passion fruit, thus much of the biochemical pathway remains unknown. In this paper a combination of organic synthesis, MS and NMR esperiments was developed in order to investigate this pathway in yellow passion fruit. The three missing stages leading to the S-cysteinylated precursor were clearly identified. Both intermediate species between S-glutathionyl and S-cysteinyl 3-mercaptohexan-1-ol were found, suggesting that the plant is capable of activating both metabolic routes. The information gained would appear to be crucial for study of this important pathway and for potentially extending this knowledge to other plants, in particular the grapevine.