Biosynthesis of the fungal metabolite, piliformic acid (2-hexylidene-3-methylsuccinic acid)

The biosynthesis of piliformic acid, a secondary metabolite of various xylariaceous fungi, has been studied in Poronia piliformis and Xylaria mali. The metabolite can be retro-biosynthetically cleaved io generate a C-8 and a C-3 moiety. The study reveals that the C-8 unit is derived directly from oc...

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Bibliographic Details
Published inJournal of the Chemical Society, Perkin Transactions 1 no. 6; pp. 827 - 834
Main Authors Chesters, NCJE, OHagan, D
Format Journal Article
LanguageEnglish
Published CAMBRIDGE Royal Soc Chemistry 1997
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
POLYKETIDE
STREPTOMYCES-CELLULOSAE
CLADOSPORIUM-CLADOSPORIOIDES
FUNGICHROMIN
FATTY-ACID
STEREOCHEMISTRY
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Summary:The biosynthesis of piliformic acid, a secondary metabolite of various xylariaceous fungi, has been studied in Poronia piliformis and Xylaria mali. The metabolite can be retro-biosynthetically cleaved io generate a C-8 and a C-3 moiety. The study reveals that the C-8 unit is derived directly from octanoate and that the octanoate in turn originates from a fatty acid synthase (FAS) rather than from a polyketide synthase (PKS). This conclusion is drawn after assaying the stereochemical course of the enoyl reductase involved in the synthesis of the octanoate unit, The C-3 unit is efficiently labelled by succinate and the-citric acid cycle intermediate oxaloacetate is implicated as a key biosynthetic precursor. The location of deuterium after isotopic labelling with sodium [H-2(15)]octanoate reveals a 1,3-hydrogen shift, indicative of a double-bond isomerisation, operating at a late stage-in the biosynthesis. A hypothesis for piliformic acid biosynthesis is presented and discussed in the context of structurally related fungal and lichen metabolites.
ISSN:1472-7781
0300-922X
1364-5463
DOI:10.1039/a606589i