Oxidative Modification Enzymes in Polyketide Biosynthetic Pathways

This article will review the recent progresses in the identification and characterization of oxidative enzymes responsible for the complex biogenesis and diversity among the chemical structures of secondary metabolites. Enzymes primarily focused in the discussion are flavin-containing monooxygenases, cytochrome P450s and α-ketoglutarate-dependent dioxygenases. The natural products discussed here differ substantially, ranging from polyketides to nonribosomal peptides to terpenoids to their complex hybrids. However, the underlying theme is related in that oxidation reactions are what drives the biosynthesis of complex structural motifs and interesting biological activities in those natural products. Specifically, the compounds discussed in this article are spirotryprostatin, aspoquinolone/penigequinolone, fumagillin, chaetoglobosin, cytochalasin, nabumetone/pentoxifylline metabolites, reveromycin, stipitatic acid (tropolone), tenellin, spliceostatin, aureothin, aurovertin, heronamide, indole vinyl isonitrile, mycinamicin, FD-891, nogalamycin, griseorhodin A, griseofulvin, cladofulvin, and lasalocid.