Get access

Cleavage of Phosphodiesters and of DNA by a Bis(guanidinium)naphthol Acting as a Metal-Free Anion Receptor

Authors

  • Dr. Stefan Ullrich,

    1. Institut für Organische Chemie und Chemische Biologie, Johann Wolfgang Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main (Germany), Fax: (+49) 69-798-29464
    Search for more papers by this author
  • Dr. Zarghun Nazir,

    1. Institut für Organische Chemie und Chemische Biologie, Johann Wolfgang Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main (Germany), Fax: (+49) 69-798-29464
    Search for more papers by this author
  • Dr. Arne Büsing,

    1. Institut für Organische Chemie und Chemische Biologie, Johann Wolfgang Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main (Germany), Fax: (+49) 69-798-29464
    Search for more papers by this author
  • Dr. Ute Scheffer,

    1. Institut für Organische Chemie und Chemische Biologie, Johann Wolfgang Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main (Germany), Fax: (+49) 69-798-29464
    Search for more papers by this author
  • Daniela Wirth,

    1. Institut für Organische Chemie und Chemische Biologie, Johann Wolfgang Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main (Germany), Fax: (+49) 69-798-29464
    Search for more papers by this author
  • Dr. Jan W. Bats,

    1. Institut für Organische Chemie und Chemische Biologie, Johann Wolfgang Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main (Germany), Fax: (+49) 69-798-29464
    Search for more papers by this author
  • Dr. Gerd Dürner,

    1. Institut für Organische Chemie und Chemische Biologie, Johann Wolfgang Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main (Germany), Fax: (+49) 69-798-29464
    Search for more papers by this author
  • Prof. Dr. Michael W. Göbel

    Corresponding author
    1. Institut für Organische Chemie und Chemische Biologie, Johann Wolfgang Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main (Germany), Fax: (+49) 69-798-29464
    • Institut für Organische Chemie und Chemische Biologie, Johann Wolfgang Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main (Germany), Fax: (+49) 69-798-29464
    Search for more papers by this author

Abstract

Phosphoric acid diesters form anions at neutral pH. As a result of charge repulsion they are notoriously resistant to hydrolysis. Nucleophilic attack, however, can be promoted by different types of electrophilic catalysts that bind to the anions and reduce their negative charge density. Although in most cases phosphodiester-cleaving enzymes and synthetic catalysts rely on Lewis acidic metal ions, some exploit the guanidinium residues of arginine as metal-free electrophiles. Here we report that a combination of two guanidines and a hydroxy group yields highly reactive receptor molecules that can attack a broad range of phosphodiester substrates by nucleophilic displacement at phosphorus in a single-turnover mode. Some stable O-phosphates were isolated and characterized further by NMR spectroscopy. The bis(guanidinium)naphthols also cleave plasmid DNA, presumably by a transphosphorylation mechanism.

Ancillary