Bioinspired strategy for the ribosomal synthesis of thioether-bridged macrocyclic peptides in bacteria

ACS Chem Biol. 2014 Sep 19;9(9):2008-13. doi: 10.1021/cb500311k. Epub 2014 Aug 1.

Abstract

Inspired by the biosynthetic logic of lanthipeptide natural products, a new methodology was developed to direct the ribosomal synthesis of macrocyclic peptides constrained by an intramolecular thioether bond. As a first step, a robust and versatile strategy was implemented to enable the cyclization of ribosomally derived peptide sequences via a chemoselective reaction between a genetically encoded cysteine and a cysteine-reactive unnatural amino acid (O-(2-bromoethyl)-tyrosine). Combination of this approach with intein-catalyzed protein splicing furnished an efficient route to achieve the spontaneous, post-translational formation of structurally diverse macrocyclic peptides in bacterial cells. The present peptide cyclization strategy was also found to be amenable to integration with split intein-mediated circular ligation, resulting in the intracellular synthesis of conformationally constrained peptides featuring a bicyclic architecture.

Publication types

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

MeSH terms

  • Amino Acid Sequence
  • Amino Acyl-tRNA Synthetases / metabolism
  • Cyclization
  • Cysteine / chemistry
  • Escherichia coli / genetics
  • Escherichia coli / metabolism
  • Inteins
  • Molecular Sequence Data
  • Mutation
  • Peptides / chemical synthesis*
  • Peptides / chemistry
  • Peptides, Cyclic / chemical synthesis*
  • Peptides, Cyclic / chemistry
  • Peptides, Cyclic / metabolism
  • Protein Biosynthesis*
  • Protein Processing, Post-Translational
  • Protein Splicing
  • Tyrosine / analogs & derivatives
  • Tyrosine / chemistry

Substances

  • Peptides
  • Peptides, Cyclic
  • Tyrosine
  • Amino Acyl-tRNA Synthetases
  • Cysteine