Diels-Alder Reactions During the Biosynthesis of Sorbicillinoids
| Autor: | Lukas Kahlert, Elizabeth Skellam, Eman F. Bassiony, Russell J. Cox |
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| Rok vydání: | 2019 |
| Předmět: |
Stereochemistry
010402 general chemistry Biosynthesis 01 natural sciences Catalysis Mixed Function Oxygenases flavin-dependent monooxygenases Fungal Proteins Polyketide chemistry.chemical_compound Aspergillus oryzae Diels alder Diels–Alder reactions Trichoderma reesei Research Articles biology Cycloaddition Reaction 010405 organic chemistry Chemistry Cyclohexanones Biological activity General Chemistry Monooxygenase biology.organism_classification 0104 chemical sciences sorbicillinoids Polyketides Hypocreales Sorbicillin Biocatalysis Epoxy Compounds Dimerization Research Article |
| Zdroj: | Angewandte Chemie (International Ed. in English) |
| ISSN: | 1521-3773 |
| Popis: | The sorbicillinoids are a class of biologically active and structurally diverse fungal polyketides arising from sorbicillin. Through co‐expression of sorA, sorB, sorC, and sorD from Trichoderma reesei QM6a, the biosynthetic pathway to epoxysorbicillinol and dimeric sorbicillinoids, which resemble Diels–Alder‐like and Michael‐addition‐like products, was reconstituted in Aspergillus oryzae NSAR1. Expression and feeding experiments demonstrated the crucial requirement of the flavin‐dependent monooxygenase SorD for the formation of dimeric sorbicillinoids, hybrid sorbicillinoids, and epoxysorbicillinol in vivo. In contrast to prior reports, SorD catalyses neither the oxidation of 2′,3′‐dihydrosorbicillin to sorbicillin nor the oxidation of sorbicillinol to oxosorbicillinol. This is the first report that both the intermolecular Diels–Alder and Michael dimerization reactions, as well as the epoxidation of sorbicillinol are catalysed in vivo by SorD. One for all: The biosynthetic pathway to dimeric sorbicillinoids and epoxysorbicillinol was reconstituted in Aspergillus oryzae NSAR1. Expression and feeding experiments demonstrated that the flavin‐dependent monooxygenase SorD catalyzes epoxidation, Diels–Alder addition, and Michael addition reactions in vivo. |
| Databáze: | OpenAIRE |
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