Direct biosynthetic cyclization of a distorted paracyclophane highlighted by double isotopic labelling of L-tyrosine

Org Biomol Chem. 2015 Mar 28;13(12):3662-6. doi: 10.1039/c5ob00114e.

Abstract

The biosynthesis of pyrrocidines, fungal PK-NRP compounds featuring a strained [9]paracyclophane, was investigated in Acremonium zeae. We used a synthetic L-tyrosine probe, labelled with oxygen 18 as a reporter of phenol reactivity and carbon 13 as a tracer of incorporation of this exogenous precursor. The ((18)O)phenolic oxygen was incorporated, suggesting that phenol behaves as a nucleophile during the formation of the bent aryl ether.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acremonium / metabolism
  • Biosynthetic Pathways
  • Chromatography, High Pressure Liquid
  • Crystallography, X-Ray
  • Cyclization
  • Heterocyclic Compounds, 4 or More Rings / chemistry
  • Isotope Labeling*
  • Mass Spectrometry
  • Piperidines / chemistry*
  • Polycyclic Compounds / chemistry*
  • Pyrrolidinones / chemistry
  • Stereoisomerism
  • Tyrosine / chemical synthesis
  • Tyrosine / chemistry
  • Tyrosine / metabolism*

Substances

  • GKK1032A-2
  • Heterocyclic Compounds, 4 or More Rings
  • Piperidines
  • Polycyclic Compounds
  • Pyrrolidinones
  • Tyrosine