Bacterial Isothiocyanate Biosynthesis by Rhodanese‐Catalyzed Sulfur Transfer onto Isonitriles
Abstract: Natural products bearing isothiocyanate (ITC) groups are an important group of specialized metabolites that play various roles in health, nutrition, and ecology. Whereas ITC biosynthesis via glucosinolates in plants has been studied in detail, there is a gap in understanding the bacterial route to specialized metabolites with such reactive heterocumulene groups, as in the antifungal sinapigladioside from Burkholderia gladioli. Here we propose an alternative ITC pathway by enzymatic sulfur transfer onto isonitriles catalyzed by rhodanese‐like enzymes (thiosulfate:cyanide sulfurtransferases). Mining the B. gladioli genome revealed six candidate genes (rhdA–F), which were individually expressed in E. coli. By means of a synthetic probe, the gene products were evaluated for their ability to produce the key ITC intermediate in the sinapigladioside pathway. In vitro biotransformation assays identified RhdE, a prototype single‐domain rhodanese, as the most potent ITC synthase. Interestingly, while RhdE also efficiently transforms cyanide into thiocyanate, it shows high specificity for the natural pathway intermediate, indicating that the sinapigladioside pathway has recruited a ubiquitous detoxification enzyme for the formation of a bioactive specialized metabolite. These findings not only elucidate an elusive step in bacterial ITC biosynthesis but also reveal a new function of rhodanese‐like enzymes in specialized metabolism.
- Location
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Deutsche Nationalbibliothek Frankfurt am Main
- Extent
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Online-Ressource
- Language
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Englisch
- Bibliographic citation
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Bacterial Isothiocyanate Biosynthesis by Rhodanese‐Catalyzed Sulfur Transfer onto Isonitriles ; day:08 ; month:12 ; year:2023 ; extent:7
ChemBioChem ; (08.12.2023) (gesamt 7)
- Creator
- DOI
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10.1002/cbic.202300732
- URN
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urn:nbn:de:101:1-2023120914093899897469
- Rights
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Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
- Last update
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15.08.2025, 7:23 AM CEST
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Deutsche Nationalbibliothek. If you have any questions about the object, please contact the data provider.
Associated
- Mlotek, Mandy D.
- Dose, Benjamin
- Hertweck, Christian
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Bacterial Isothiocyanate Biosynthesis by Rhodanese‐Catalyzed Sulfur Transfer onto Isonitriles
Funktionalisierte Vinyloxirane durch reduktive Allylierung von Estern : stereoselektive Synthesen von Lamoxiren und Sphingoidbasen
Biosynthesis of Sinapigladioside, an Antifungal Isothiocyanate from Burkholderia Symbionts
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A Type III Polyketide Synthase Specific for Sporulating Negativicutes is Responsible for Alkylpyrone Biosynthesis
Photosensitizers Enable the Formation of Biphenyls with UV‐LEDs and Sunlight
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Discovery and biosynthesis of the redox cofactor mycofactocin
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