Configurational assignment of cyclic peroxy metabolites provides an insight into their biosynthesis: Isolation of plakortolides, seco-plakortolides, and plakortones from the Australian marine sponge Plakinastrella clathrata

Yong, Ken W. L., De Voss, James J., Hooper, John N. A. and Garson, Mary J. (2011) Configurational assignment of cyclic peroxy metabolites provides an insight into their biosynthesis: Isolation of plakortolides, seco-plakortolides, and plakortones from the Australian marine sponge Plakinastrella clathrata. Journal of Natural Products, 74 2: 194-207. doi:10.1021/np100620x


Author Yong, Ken W. L.
De Voss, James J.
Hooper, John N. A.
Garson, Mary J.
Title Configurational assignment of cyclic peroxy metabolites provides an insight into their biosynthesis: Isolation of plakortolides, seco-plakortolides, and plakortones from the Australian marine sponge Plakinastrella clathrata
Journal name Journal of Natural Products   Check publisher's open access policy
ISSN 0163-3864
1520-6025
Publication date 2011-02
Year available 2011
Sub-type Article (original research)
DOI 10.1021/np100620x
Volume 74
Issue 2
Start page 194
End page 207
Total pages 14
Place of publication Washigton DC, United States
Publisher American Chemical Society
Collection year 2012
Language eng
Formatted abstract
Sixteen new compounds, comprising nine new plakortolides K-S (1-9), four seco-plakortolides (10-13), and three plakortones (14-16), were isolated from the Australian sponge Plakinastrella clathrata. Structural elucidation, including relative configurational assignment, was based on extensive spectroscopic analysis, while the absolute configurations of 1-4 were deduced from 1H NMR analyses on MPA esters derived from Zn/AcOHreduction products. Diastereomeric sets of plakortolides, e.g., K and L, orMand N, differed in configuration at C-3/C-4 rather than at C-6, a stereochemical result that compromises a biosynthetic pathway involving Diels-Alder cycloaddition of molecular oxygen to a Δ3,5-diunsaturated fatty acid precursor. The biosynthesis may plausibly involve cyclization of a 6-hydroperoxydienoic acid intermediate following stereospecific introduction of the hydroperoxy group into a polyketide-derived precursor. Isolated seco-plakortolides converted under mild conditions into plakortones with full retention of configuration, suggesting C-6 hydroxy attack on an R,β-unsaturated lactone intermediate. The NMR data reported for the compound named plakortolide E are inconsistent with the current literature structure and are those of the corresponding secoplakortolide (19). The reported conversion of the metabolite into a plakortone ether on storage is consistent with this structural
revision.
Keyword Polyketide-peroxides
Bioactive cycloperoxides
Genus plakortis
Simplex
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ
Additional Notes Publication Date (Web): January 24, 2011

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2012 Collection
School of Chemistry and Molecular Biosciences
 
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Created: Sun, 20 Mar 2011, 00:08:37 EST