Biosynthesis of para- Cyclophane-Containing Hirsutellone Family of Fungal Natural Products

J Am Chem Soc. 2021 Apr 21;143(15):5605-5609. doi: 10.1021/jacs.1c00098. Epub 2021 Apr 9.

Abstract

Hirsutellones are fungal natural products containing a macrocyclic para-cyclophane connected to a decahydrofluorene ring system. We have elucidated the biosynthetic pathway for pyrrocidine B (3) and GKK1032 A2 (4). Two small hypothetical proteins, an oxidoreductase and a lipocalin-like protein, function cooperatively in the oxidative cyclization of the cyclophane, while an additional hypothetical protein in the pyrrocidine pathway catalyzes the exo-specific cycloaddition to form the cis-fused decahydrofluorene.

Publication types

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

MeSH terms

  • Acremonium / chemistry
  • Acremonium / metabolism
  • Biological Products / chemistry
  • Biological Products / metabolism*
  • Bridged-Ring Compounds / chemistry
  • Bridged-Ring Compounds / metabolism*
  • Catalysis
  • Cycloaddition Reaction
  • Fungi / chemistry*
  • Fungi / metabolism
  • Heterocyclic Compounds, 4 or More Rings / chemistry
  • Heterocyclic Compounds, 4 or More Rings / metabolism*
  • Hypocreales / chemistry
  • Hypocreales / metabolism
  • Molecular Conformation
  • Oxidation-Reduction
  • Oxidoreductases / metabolism
  • Pyrrolidinones / chemistry
  • Pyrrolidinones / metabolism*
  • Stereoisomerism

Substances

  • Biological Products
  • Bridged-Ring Compounds
  • GKK1032A-2
  • Heterocyclic Compounds, 4 or More Rings
  • Pyrrolidinones
  • hirsutellone B
  • pyrrocidine B
  • Oxidoreductases