Chemoselective Covalent Modification of K-Ras(G12R) with a Small Molecule Electrophile

J Am Chem Soc. 2022 Sep 7;144(35):15916-15921. doi: 10.1021/jacs.2c05377. Epub 2022 Aug 24.

Abstract

KRAS mutations are one of the most common oncogenic drivers in human cancer. While small molecule inhibitors for the G12C mutant have been successfully developed, allele-specific inhibition for other KRAS hotspot mutants remains challenging. Here we report the discovery of covalent chemical ligands for the common oncogenic mutant K-Ras(G12R). These ligands bind in the Switch II pocket and irreversibly react with the mutant arginine residue. An X-ray crystal structure reveals an imidazolium condensation product formed between the α,β-diketoamide ligand and the ε- and η-nitrogens of arginine 12. Our results show that arginine residues can be selectively targeted with small molecule electrophiles despite their weak nucleophilicity and provide the basis for the development of mutant-specific therapies for K-Ras(G12R)-driven cancer.

Publication types

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

MeSH terms

  • Arginine
  • Genes, ras
  • Humans
  • Ligands
  • Mutation
  • Neoplasms*
  • Proto-Oncogene Proteins p21(ras)* / genetics

Substances

  • Ligands
  • Arginine
  • Proto-Oncogene Proteins p21(ras)