Stable Cu (I) Complexes for Intracellular Cu-Catalyzed Azide Alkyne Cycloaddition

Chemistry. 2024 Dec 23;30(72):e202402887. doi: 10.1002/chem.202402887. Epub 2024 Nov 20.

Abstract

The copper-catalyzed azide-alkyne cycloaddition (CuAAC) has heralded a new era of chemical biology and biomedicine. However, caveats of the CuAAC include formation of reactive oxygen species (ROS) and other copper-related toxicity. This limits utility in sensitive biological samples and matrices. Towards addressing these caveats, we synthesized and fully characterized two air and water stable trinuclear Cu(I) dimer complexes. The complexes were stable to oxidation in the presence of hydrogen peroxideand other chelators, which was reasoned to be due to the linear benzimidazole-Cu-benzimidazole geometry. Computational investigations of the catalytic cycle implicated two of the three coppers in the trimer complex as the active metal centers. The complexes were shown to catalyze the reaction at far below sub-toxic concentrations for intracellular click reactions to label triple negative breast cancer cells and compared to the current CuSO4-THPTA standard.

Keywords: Bioorthogonal Chemistry; Click Chemistry; Linear Cu (I); Stable Cu (I) Complexes.

MeSH terms

  • Alkynes* / chemistry
  • Azides* / chemistry
  • Catalysis
  • Cell Line, Tumor
  • Click Chemistry
  • Coordination Complexes* / chemistry
  • Copper* / chemistry
  • Cycloaddition Reaction*
  • Humans
  • Oxidation-Reduction
  • Reactive Oxygen Species / metabolism
  • Triple Negative Breast Neoplasms / drug therapy

Substances

  • Copper
  • Azides
  • Alkynes
  • Coordination Complexes
  • Reactive Oxygen Species