N-->S phosphoryl migration in phosphoryl glutathion.
It was found that in the case of N-(diisopropylphosphoryl) glutathion (reduced form), 2, N-->S phosphoryl migration took place, but not for N,N-bis(diisopropylphosphoryl) glutathion (oxidized form) or N-diisopropylphosphoryl cysteine. These results were deduced by 31P-NMR tracing experiments. It was shown that phosphoryl migration was catalyzed by an intramolecular carboxyl group, and a mechanism involving a mixed carboxyl-phosphoric anhydride was proposed. A competitive reaction between the amino and thiol group toward diisopropyl phosphite indicated that the phospho-thiol derived from N-(diisopropylphosphoryl) glutathion (reduced form), 2, did not result from direct phosphorylation of the thiol group. N,S-Bis(diisopropylphosphoryl) glutathion provides an authentic sample to confirm the migrated phosphoryl thiol product.
Yang
H J
HJ
Department of Chemistry, Tsinghua University, Beijing, People's Republic of China.
Liu
J
J
Zhao
Y F
YF
D000595:Amino Acid Sequence; D003545:Cysteine / Q000031:analogs & derivatives / Q000138:chemical synthesis / Q000737:chemistry; D005978:Glutathione / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008969:Molecular Sequence Data; D015394:Molecular Structure; D009842:Oligopeptides / Q000138:chemical synthesis / Q000737:chemistry; D010084:Oxidation-Reduction; D010766:Phosphorylation; D016339:Spectrometry, Mass, Fast Atom Bombardment
D009842:Oligopeptides; D005978:Glutathione; D003545:Cysteine