Comparative biochemistry of fatty acid and macrolide antibiotic (brefeldin A). Formation in Penicillium brefeldianum

Article abstract of DOI:10.1016/S0040-4020(01)88660-9

The stereochemistry of the D labeling of mycelial steric and oleic acids by ¹³C²H₃CO₂H in vivo in Penicillium brefeldianum is the same at their even numbered, non-starting group positions as found for saturated fatty acid biosynthesis in two other eukaryotes. This conclusion was reached by comparing the D labeling at C-10 of methyl stearate with that of methyl oleate as determined by ¹³C NMR spectroscopy. Since brefeldin A is labeled by CD₃CO₂H at C-6 and C-8 with the enantiotopic configurational result, the stereochemistry of antibiotic formation either differs at two points from fatty acid formation; or the C-6 and C-8 configuration of 1 is determined by some process unique to cyclopentane ring formation, but not by reduction of enolylthioester intermediates of its carbon chain assembly process.