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Cleavage of Phosphodiesters and of DNA by a Bis(guanidinium)naphthol Acting as a Metal‐Free Anion Receptor
Author(s) -
Ullrich Stefan,
Nazir Zarghun,
Büsing Arne,
Scheffer Ute,
Wirth Daniela,
Bats Jan W.,
Dürner Gerd,
Göbel Michael W.
Publication year - 2011
Publication title -
chembiochem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.05
H-Index - 126
eISSN - 1439-7633
pISSN - 1439-4227
DOI - 10.1002/cbic.201100022
Subject(s) - phosphodiester bond , chemistry , nucleophile , electrophile , hydrolysis , combinatorial chemistry , stereochemistry , catalysis , nuclear magnetic resonance spectroscopy , cleavage (geology) , organic chemistry , biochemistry , rna , geotechnical engineering , fracture (geology) , engineering , gene
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.