Perfluoroaryl Azide Staudinger Reaction: A Fast and Bioorthogonal Reaction

Angew Chem Int Ed Engl. 2017 Sep 25;56(40):12117-12121. doi: 10.1002/anie.201705346. Epub 2017 Sep 1.

Abstract

We report a fast Staudinger reaction between perfluoroaryl azides (PFAAs) and aryl phosphines, which occurs readily under ambient conditions. A rate constant as high as 18 m-1 s-1 was obtained between methyl 4-azido-2,3,5,6-tetrafluorobenzoate and methyl 2-(diphenylphosphanyl)benzoate in CD3 CN/D2 O. Furthermore, the iminophosphorane product was stable toward hydrolysis and aza-phosphonium ylide reactions. This PFAA Staudinger reaction proved to be an excellent bioothorgonal reaction. PFAA-derivatized mannosamine and galactosamine were successfully transformed into cell-surface glycans and efficiently labeled with phosphine-derivatized fluorophore-conjugated bovine serum albumin.

Keywords: Staudinger reaction; bioconjugation; bioorthogonal reactions; metabolic labelling; perfluoroaryl azides.

Publication types

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

MeSH terms

  • Azides / chemistry*
  • Fluorescent Dyes / chemistry
  • Fluorine Compounds / chemistry*
  • Hydrolysis
  • Kinetics
  • Microscopy, Fluorescence
  • Phosphines / chemistry*
  • Polysaccharides / chemistry
  • Proton Magnetic Resonance Spectroscopy

Substances

  • Azides
  • Fluorescent Dyes
  • Fluorine Compounds
  • Phosphines
  • Polysaccharides
  • phosphine