Model Reaction of Tyrosinase. Oxygenation Mechanism of Phenols by Dinuclear Copper-Dioxygen Complexes.

Accession number;02A0304395
Title;Model Reaction of Tyrosinase. Oxygenation Mechanism of Phenols by Dinuclear Copper-Dioxygen Complexes.
Author; ITO SHINOBU (Osaka City Univ., Grad. Sch.) KUMEI HIDEYUKI (Osaka Univ., Grad. Sch.) TAKI MASAYASU (Osaka Univ., Grad. Sch.) TACHI YOSHIMITSU (Osaka City Univ., Grad. Sch.) FUKUZUMI SHUN'ICHI (Osaka Univ., Grad. Sch.)
Journal Title;Abstracts. Symposium on Biofunctional Chemistry
Journal Code:L0836A
ISSN:
VOL.16th;NO.;PAGE.78-79(2001)
Figure&Table&Reference;
Pub. Country;Japan
Language;Japanese
Abstract;Efficient conversion of phenol derivatives to the corresponding catechols has been achieved for the first time by intermolecular reactions of a (.MU.-.ETA.2:.ETA.2-peroxo)dicopper(II) complex, supported by tridentate ligand L (N,N-bis[2-(2-pyridyl)ethyl]-.ALPHA.,.ALPHA.-dideuteriobenzyl-amine), with lithium salts of phenolates. The mechanistic studies on the catechol formation have been performed to indicate that the oxygenation of phenolates to the corresponding catechols by the (.MU.-.ETA.2:.ETA.2-peroxo)dicopper(II) complex proceeds via an electrophilic aromatic substitution mechanism, where the oxygenation of the substrate (C-O bond formation) occurs along with the O-O bond cleavage of the peroxo intermediate. These results will provide valuable mechanistic insight into the phenolase activity of tyrosinase. (author abst.)