Genome-based characterization of two prenylation steps in the assembly of the stephacidin and notoamide anticancer agents in a marine-derived Aspergillus sp

J Am Chem Soc. 2010 Sep 15;132(36):12733-40. doi: 10.1021/ja1049302.

Abstract

Stephacidin and notoamide natural products belong to a group of prenylated indole alkaloids containing a core bicyclo[2.2.2]diazaoctane ring system. These bioactive fungal secondary metabolites have a range of unusual structural and stereochemical features but their biosynthesis has remained uncharacterized. Herein, we report the first biosynthetic gene cluster for this class of fungal alkaloids based on whole genome sequencing of a marine-derived Aspergillus sp. Two central pathway enzymes catalyzing both normal and reverse prenyltransfer reactions were characterized in detail. Our results establish the early steps for creation of the prenylated indole alkaloid structure and suggest a scheme for the biosynthesis of stephacidin and notoamide metabolites. The work provides the first genetic and biochemical insights for understanding the structural diversity of this important family of fungal alkaloids.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Animals
  • Antineoplastic Agents / chemistry
  • Antineoplastic Agents / metabolism*
  • Aspergillus / genetics*
  • Aspergillus / metabolism
  • Biological Factors / biosynthesis*
  • Biological Factors / chemistry
  • Biological Factors / metabolism
  • Genome*
  • Indole Alkaloids / chemistry
  • Indole Alkaloids / metabolism*
  • Molecular Conformation
  • Prenylation
  • Stereoisomerism

Substances

  • Antineoplastic Agents
  • Biological Factors
  • Indole Alkaloids
  • notoamide B
  • stephacidin A