Total synthesis of daptomycin by cyclization via a chemoselective serine ligation

J Am Chem Soc. 2013 Apr 24;135(16):6272-9. doi: 10.1021/ja4012468. Epub 2013 Apr 16.

Abstract

A total synthesis of daptomycin, the first natural product antibiotic launched in a generation, was achieved. This convergent synthesis relies on an efficient macrocyclization via a serine ligation to assemble the 31-membered cyclic depsipeptide. The difficult esterification by the nonproteinogenic amino acid kynurenine was accomplished via the esterification of a threonine residue by a suitably protected Trp ester, followed by ozonolysis. This synthesis provides a foundation and framework to prepare varied analogues of daptomycin to establish its structure-activity profile.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Amino Acids / chemistry
  • Anti-Bacterial Agents / chemical synthesis*
  • Cyclization
  • Daptomycin / chemical synthesis*
  • Indicators and Reagents
  • Kynurenine / chemistry
  • Lactams / chemical synthesis
  • Lactams / chemistry
  • Ligands
  • Ozone / chemistry
  • Serine / chemistry*
  • Structure-Activity Relationship
  • Threonine / chemistry

Substances

  • Amino Acids
  • Anti-Bacterial Agents
  • Indicators and Reagents
  • Lactams
  • Ligands
  • Threonine
  • Kynurenine
  • Serine
  • Ozone
  • Daptomycin