Abstract

AbstractWe uncovered and reconstituted a concise biosynthetic pathway of the strained dipeptide (+)‐azonazine A from marine‐derived Aspergillus insulicola. Formation of the hexacyclic benzofuranoindoline ring system from cyclo‐(l‐Trp‐N‐methyl‐l‐Tyr) is catalyzed by a P450 enzyme through an oxidative cyclization. Supplementing the producing strain with various indole‐substituted tryptophan derivatives resulted in the generation of a series of azonazine A analogs.

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