A Fungal N‐Dimethylallyltryptophan Metabolite from Fusarium fujikuroi

• Published in: Chembiochem : a European journal of chemical biology Vol. 18; no. 10; pp. 899 - 904
• Main Authors: Arndt, Birgit, Janevska, Slavica, Schmid, Robin, Hübner, Florian, Tudzynski, Bettina, Humpf, Hans‐Ulrich
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 18.05.2017; Wiley Subscription Services, Inc
• Subjects: alkaloids; Alkyl and Aryl Transferases - metabolism; Biochemistry & Molecular Biology; Biosynthesis; Chemistry, Medicinal; Fungal Proteins - metabolism; Fungi; Fusarium; Fusarium - metabolism; Fusarium fujikuroi; Genes; Genomes; In vivo methods and tests; Life Sciences & Biomedicine; mass spectrometry; Metabolites; natural products; NMR spectroscopy; Oryza - microbiology; Peptides; Pharmacology & Pharmacy; Polyketides; Prenylation; Science & Technology; Secondary metabolites; Side reactions; Terpenes; Tryptophan; Tryptophan - metabolism; ASPERGILLUS-FUMIGATUS; alkaloids; 7-DIMETHYLALLYLTRYPTOPHAN SYNTHASE; PRENYLTRANSFERASE; CYCLIC-PEPTIDES; natural products; CYCLOMARINS; GENE; CATALYZES; PRODUCTS; biosynthesis; PURIFICATION; mass spectrometry; NMR spectroscopy
• ISSN: 1439-4227; 1439-7633
• DOI: 10.1002/cbic.201600691

The range of secondary metabolites (SMs) produced by the rice pathogen Fusarium fujikuroi is quite broad. Several polyketides, nonribosomal peptides and terpenes have been identified. However, no products of dimethylallyltryptophan synthases (DMATSs) have been elucidated, although two putative DMATS genes are present in the F. fujikuroi genome. In this study, the in vivo product derived from one of the DMATSs (DMATS1, FFUJ_09179) was identified with the help of the software MZmine 2. Detailed structure elucidation showed that this metabolite is a reversely N‐prenylated tryptophan with a rare form of prenylation. Further identified products probably resulted from side reactions of DMATS1. The genes adjacent to DMATS1 were analyzed; this showed no influence on the biosynthesis of the product. The secondary metabolite of FFUJ_09179 (encoding the dimethylallyltryptophan synthase DMATS1) was identified in vivo as reversely N‐prenylated tryptophan. Besides this main product, several putative shunt products were found. The corresponding gene cluster was analyzed, showing no influence on the production of the DMATS‐metabolite.