Total Biosynthesis of Brassicicenes: Identification of a Key Enzyme for Skeletal Diversification.

The biosynthetic pathway of brassicicenes, derived from the phytopathogen Pseudocercospora fijiensis, was fully reconstituted. Heterologous expression of the eight genes highly expressed in infected leaf tissues generated a new brassicicene derivative as a final product. Together with the characterization of P450 from Alternaria brassicicola, a late stage of the biosynthetic pathway, which generates remarkable structural diversity, has been proposed. Notably, a unique P450 that converts 3 to the structurally distinct 4 and 6 was identified.