Coulombic effects on the traceless Staudinger ligation in water

Bioorg Med Chem. 2009 Feb 1;17(3):1055-63. doi: 10.1016/j.bmc.2008.02.047. Epub 2008 Feb 16.

Abstract

The traceless Staudinger ligation can be mediated by phosphinothiols under physiological conditions. Proximal positive charges are necessary to achieve that transformation, presumably because those charges discourage protonation of the key iminophosphorane intermediate. Here, a series of cationic phosphinothiols is used to probe Coulombic effects on the traceless Staudinger ligation in aqueous buffers. The reagent bis(m-N,N-dimethylaminomethylphenyl)phosphinomethanethiol (3) is found to be superior to others, both in its ability to mediate the traceless Staudinger ligation in water and in the efficiency of its synthesis.

Publication types

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

MeSH terms

  • Magnetic Resonance Spectroscopy
  • Organothiophosphorus Compounds / chemical synthesis
  • Organothiophosphorus Compounds / chemistry*
  • Peptides / chemical synthesis
  • Peptides / chemistry
  • Phenylenediamines / chemical synthesis
  • Phenylenediamines / chemistry*
  • Sulfhydryl Compounds / chemical synthesis
  • Sulfhydryl Compounds / chemistry*
  • Water / chemistry*

Substances

  • Organothiophosphorus Compounds
  • Peptides
  • Phenylenediamines
  • Sulfhydryl Compounds
  • bis(m-N,N-dimethylaminomethylphenyl)phosphinomethanethiol
  • Water