Kandziora, Nadine; Andexer, Jennifer N.; Moss, Steven J.; Wilkinson, Barrie; Leadlay, Peter F.; Hahn, Frank: Uncovering the origin of Z-configured double bonds in polyketides: intermediate E-double bond formation during borrelidin biosynthesis. In: Chemical Science 5 (2014), Nr. 9, S. 3563-3567. DOI:
http://dx.doi.org/10.1039/c4sc00883a
Zusammenfassung: |
Formation of Z-configured double bonds in reduced polyketides is uncommon and their origins have not been extensively studied. To investigate the origin of the Z-configured double bond in the macrolide borrelidin, the recombinant dehydratase domains BorDH2 and B0rDH3 were assayed with a synthetic analogue of the predicted tetraketide substrate. The configuration of the dehydrated products was determined to be E in both cases by comparison to synthetic standards. Detailed NMR spectroscopic analysis of the biosynthetic intermediate pre-borrelidin confirmed the E,E-configuration of the fulllength polyketide synthase product. In contrast to a previously-proposed hypothesis, our results show that in this case the Z-configured double bond is not formed via dehydration from a 3 L-configured precursor, but rather as the result of a later isomerization process.
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Lizenzbestimmungen: |
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Publikationstyp: |
Article |
Publikationsstatus: |
publishedVersion |
Erstveröffentlichung: |
2014-06-30 |
Schlagwörter (englisch): |
Angiogenesis Inhibitor Borrelidin, Synthase Ketoreductase Domain, Streptomyces-Parvulus TU4055, Dehydratase Domain, Gene-Cluster, In-Vitro, Stereospecificity, Crystal, Stereochemistry, (-)-borrelidin, Borrelidin
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Fachliche Zuordnung (DDC): |
540 | Chemie
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