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Desertomycin A is an aminopolyol polyketide containing a macrolactone ring. We have proposed that desertomycin A and similar compounds (marginolactones) are formed by polyketide synthases primed not with γ‐aminobutanoyl‐CoA but with 4‐guanidinylbutanoyl‐CoA, to avoid facile cyclization of the starter unit. This hypothesis requires that there be a final‐stage de‐amidination of the corresponding guanidino‐substituted...
Tetrahydropyran rings are a common feature of complex polyketide natural products, but much remains to be learned about the enzymology of their formation. The enzyme SalBIII from the salinomycin biosynthetic pathway resembles other polyether epoxide hydrolases/cyclases of the MonB family, but SalBIII plays no role in the conventional cascade of ring opening/closing. Mutation in the salBIII gene gave...
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