Heterologous Biosynthesis of Nodulisporic Acid F

J Am Chem Soc. 2018 Jan 17;140(2):582-585. doi: 10.1021/jacs.7b10909. Epub 2018 Jan 8.

Abstract

Nodulisporic acids comprise a group of valuable indole diterpenes that exhibit potent insecticidal activities. We report the identification of a gene cluster in the genome of the filamentous fungus Hypoxylon pulicicidum (Nodulisporium sp.) that contains genes responsible for the biosynthesis of nodulisporic acids. Using Penicillium paxilli as a heterologous host, and through pathway reconstitution experiments, we identified the function of four genes involved in the biosynthesis of the nodulisporic acid core compound, nodulisporic acid F (NAF). Two of these genes (nodM and nodW) are especially significant as they encode enzymes with previously unreported functionality: nodM encodes a 3-geranylgeranylindole epoxidase capable of catalyzing only a single epoxidation step to prime formation of the distinctive ring structure of nodulisporic acids, and nodW encodes the first reported gene product capable of introducing a carboxylic acid moiety to an indole diterpene core structure that acts as a reactive handle for further modification. Here, we present the enzymatic basis for the biosynthetic branch point that gives rise to nodulisporic acids.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Fungi* / genetics
  • Fungi* / metabolism
  • Indoles / chemistry*
  • Molecular Structure
  • Penicillium / chemistry
  • Penicillium / genetics
  • Penicillium / metabolism

Substances

  • Indoles
  • nodulisporic acid F