Total synthesis, characterization, and conformational analysis of the naturally occurring hexadecapeptide integramide A and a diastereomer

Chemistry. 2010 Jan 4;16(1):316-27. doi: 10.1002/chem.200900945.

Abstract

Integramide A is a 16-amino acid peptide inhibitor of the enzyme HIV-1 integrase. We have recently reported that the absolute stereochemistries of the dipeptide sequence near the C terminus are L-Iva(14)-D-Iva(15). Herein, we describe the syntheses of the natural compound and its D-Iva(14)-L-Iva(15) diastereomer, and the results of their chromatographic/mass spectrometric analyses. We present the conformational analysis of the two compounds and some of their synthetic intermediates of different main-chain length in the crystal state (by X-ray diffraction) and in solvents of different polarities (using circular dichroism, FTIR absorption, and 2D NMR techniques). These data shed light on the mechanism of inhibition of HIV-1 integrase, which is an important target for anti-HIV therapy.

MeSH terms

  • Amino Acid Sequence
  • Circular Dichroism
  • Dipeptides / chemistry*
  • HIV Integrase / metabolism*
  • HIV Integrase Inhibitors / chemical synthesis*
  • HIV Integrase Inhibitors / chemistry
  • HIV Integrase Inhibitors / pharmacology*
  • HIV-1 / drug effects*
  • Humans
  • Magnetic Resonance Spectroscopy
  • Models, Molecular
  • Molecular Conformation
  • Molecular Sequence Data
  • Oligopeptides / chemical synthesis*
  • Oligopeptides / chemistry
  • Oligopeptides / pharmacology*
  • Peptide Fragments
  • Peptides / chemical synthesis*
  • Peptides / chemistry
  • Stereoisomerism
  • X-Ray Diffraction

Substances

  • Dipeptides
  • HIV Integrase Inhibitors
  • Oligopeptides
  • Peptide Fragments
  • Peptides
  • integramide A
  • HIV Integrase