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
Abstract: |
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.
|
License of this version: |
Es gilt deutsches Urheberrecht. Das Dokument darf zum eigenen Gebrauch kostenfrei genutzt, aber nicht im Internet bereitgestellt oder an Außenstehende weitergegeben werden. Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich. |
Publication type: |
Article |
Publishing status: |
publishedVersion |
Publication date: |
2014-06-30 |
Keywords english: |
Angiogenesis Inhibitor Borrelidin, Synthase Ketoreductase Domain, Streptomyces-Parvulus TU4055, Dehydratase Domain, Gene-Cluster, In-Vitro, Stereospecificity, Crystal, Stereochemistry, (-)-borrelidin, Borrelidin
|
DDC: |
540 | Chemie
|