Structural examination of ring-closing metathesis-derived 15-member macrocycles as Grb2 SH2 domain-binding tetrapeptide mimetics

J Org Chem. 2007 Dec 7;72(25):9635-42. doi: 10.1021/jo701831q. Epub 2007 Nov 9.

Abstract

Ring-closing metathesis (RCM) was employed to join carboxy-terminal alkenyl glycine side chains together with vinyl- and allyl-functionality appended to the beta-methylene of amino-terminal phosphotyrosyl (pTyr) mimetics. This required the synthesis of a variety of new pTyr mimetics, including a novel aza-containing analogue. Many of the resulting 15-member macrocyclic tetrapeptide mimetics exhibited low nanomolar Grb2 SH2 domain-binding affinities in spite of the fact that differing ring junction stereochemistries and geometries of the RCM-derived double bond were employed. The finding that significant latitude exists in the structural requirements for ring closure may facilitate the development of therapeutically relevant macrocyle-based Grb2 SH2 domain-binding antagonists. The synthetic approaches used in this study may also find application to peptide mimetics directed at other biological targets.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, N.I.H., Intramural

MeSH terms

  • Binding Sites
  • Cyclization
  • GRB2 Adaptor Protein / chemistry*
  • Macrocyclic Compounds / chemical synthesis*
  • Macrocyclic Compounds / chemistry*
  • Molecular Conformation
  • Molecular Mimicry
  • Oligopeptides / chemical synthesis*
  • Oligopeptides / chemistry*
  • Stereoisomerism
  • src Homology Domains

Substances

  • GRB2 Adaptor Protein
  • Macrocyclic Compounds
  • Oligopeptides