A Monooxygenase from Boreostereum vibrans Catalyzes Oxidative Decarboxylation in a Divergent Vibralactone Biosynthesis Pathway

Angew Chem Int Ed Engl. 2016 Apr 25;55(18):5463-6. doi: 10.1002/anie.201510928. Epub 2016 Mar 23.

Abstract

The oxidative decarboxylation of prenyl 4-hydroxybenzoate to prenylhydroquinone has been frequently proposed for the biosynthesis of prenylated (hydro)quinone derivates (sometimes meroterpenoids), yet no corresponding genes or enzymes have so far been reported. A FAD-binding monooxygenase (VibMO1) was identified that converts prenyl 4-hydroxybenzoate into prenylhydroquinone and is likely involved in the biosynthesis of vibralactones and other meroterpenoids in the basidiomycete Boreostereum vibrans. Feeding of 3-allyl-4-hydroxybenzylalcohol, an analogue of the vibralactone pathway intermediate 3-prenyl-4-hydroxybenzylalcohol, generated 20 analogues with different scaffolds. This demonstrated divergent pathways to skeletally distinct compounds initiating from a single precursor, thus providing the first insight into a novel biosynthetic pathway for 3-substituted γ-butyrolactones from a shikimate origin.

Keywords: biosynthesis; decarboxylation; enzymes; meroterpenoid; natural products.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Basidiomycota / chemistry
  • Basidiomycota / enzymology*
  • Basidiomycota / metabolism
  • Biosynthetic Pathways*
  • Decarboxylation
  • Hydroquinones / metabolism
  • Lactones / analysis
  • Lactones / metabolism*
  • Mixed Function Oxygenases / metabolism*
  • Parabens / metabolism

Substances

  • Hydroquinones
  • Lactones
  • Parabens
  • vibralactone
  • Mixed Function Oxygenases
  • 4-hydroxybenzoic acid
  • hydroquinone