P450-Mediated Coupling of Indole Fragments To Forge Communesin and Unnatural Isomers

J Am Chem Soc. 2016 Mar 30;138(12):4002-5. doi: 10.1021/jacs.6b01413. Epub 2016 Mar 18.

Abstract

Dimeric indole alkaloids are structurally diverse natural products that have attracted significant attention from the synthetic and biosynthetic communities. Here, we describe the characterization of a P450 monooxygenase CnsC from Penicillium that catalyzes the heterodimeric coupling between two different indole moieties, tryptamine and aurantioclavine, to construct vicinal quaternary stereocenters and yield the heptacyclic communesin scaffold. We show, via biochemical characterization, substrate analogues, and computational methods that CnsC catalyzes the C3-C3' carbon-carbon bond formation and controls the regioselectivities of the pair of subsequent aminal bond formations to yield the communesin core. Use of ω-N-methyltryptamine and tryptophol in place of tryptamine led to the enzymatic synthesis of isocommunesin compounds, which have not been isolated to date.

Publication types

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

MeSH terms

  • Cytochrome P-450 Enzyme System / chemistry
  • Cytochrome P-450 Enzyme System / metabolism*
  • Heterocyclic Compounds, 4 or More Rings / chemical synthesis
  • Heterocyclic Compounds, 4 or More Rings / chemistry*
  • Heterocyclic Compounds, 4 or More Rings / metabolism*
  • Indoles / chemistry
  • Indoles / metabolism*
  • Isomerism
  • Molecular Structure

Substances

  • Heterocyclic Compounds, 4 or More Rings
  • Indoles
  • communesin A
  • indole
  • Cytochrome P-450 Enzyme System