The cyanobacterial dialkylresorcinol bartolosides were initially reported to feature glycosylated and halogenated moieties. Later, biosynthetic and studies showed that the chlorinated alkyl chains are utilized for a nucleophilic substitution with free fatty acid carboxylates from primary metabolism, generating bartoloside esters. Here, we applied a workflow based on PCR screening coupled to LC-HRESIMS and molecular network analysis with the aim of discovering additional bartoloside diversity. We report the annotation of 27 bartoloside and bartoloside ester derivatives, including the characterization of two new bartolosides, underlining the breadth of structures generated by bartoloside biosynthetic pathways. Some of the herein reported bartolosides feature hydroxylation in their side chains, a modification that has not been associated with this metabolite family.
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http://dx.doi.org/10.1021/acs.jnatprod.4c00832 | DOI Listing |
J Nat Prod
December 2024
CIIMAR - Interdisciplinary Centre of Marine and Environmental Research, University of Porto, Matosinhos 4450-208, Portugal.
BMC Genomics
August 2021
Interdisciplinary Centre of Marine and Environmental Research (CIIMAR/CIMAR), University of Porto, Matosinhos, Portugal.
Background: Halogenation is a recurring feature in natural products, especially those from marine organisms. The selectivity with which halogenating enzymes act on their substrates renders halogenases interesting targets for biocatalyst development. Recently, CylC - the first predicted dimetal-carboxylate halogenase to be characterized - was shown to regio- and stereoselectively install a chlorine atom onto an unactivated carbon center during cylindrocyclophane biosynthesis.
View Article and Find Full Text PDFNat Prod Rep
October 2019
Interdisciplinary Centre of Marine and Environmental Research (CIIMAR/CIMAR), University of Porto, Matosinhos, Portugal.
Covering: up to 2019 Alkylresorcinols are amphiphilic metabolites, well-known for their diverse biological activities, produced by both prokaryotes and eukaryotes. A few classes of alkylresorcinol scaffolds have been reported from the photoautotrophic cyanobacteria, ranging from the relatively simple hierridins to the more intricate cylindrocyclophanes. Recently, it has emerged that cyanobacteria employ two different biosynthetic pathways to produce unique alkylresorcinol scaffolds.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2015
Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge MA, 02138 (USA).
The isolation of the bartolosides, unprecedented cyanobacterial glycolipids featuring aliphatic chains with chlorine substituents and C-glycosyl moieties, is reported. Their chlorinated dialkylresorcinol (DAR) core presented a major structural-elucidation challenge. To overcome this, we discovered the bartoloside (brt) biosynthetic gene cluster and linked it to the natural products through in vitro characterization of the DAR-forming ketosynthase and aromatase.
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