TY - JOUR
T1 - Theoretical studies on ortho-oxidation of phenols with dioxygen mediated by dicopper complex
T2 - Hints for a catalyst with the phenolase activity of tyrosinase
AU - Naka, Hiroshi
AU - Kondo, Yoshinori
AU - Usui, Shinya
AU - Hashimoto, Yuichi
AU - Uchiyama, Masanobu
PY - 2007/3
Y1 - 2007/3
N2 - Theoretical studies on the chemo- and regioselective. ortho-oxidation reaction of phenols mediated by a biomimetic (μ-η2: 2peroxo)dicopper(II) complex were performed using unrestricted hybrid density functional theory (UB3LYP) calculations, with the aim of providing a guide for the development of new bio-inspired catalysts with the phenolase activity of tyrosinase. Energetic, structural, and electronic analyses suggested the involvement of a side-on (μ-2:2)-Cu 2O2 complex as an active intermediate, and a single electron transfer (SET)-induced electrophilic aromatic substitution mechanism is proposed for the rate-determining C-O bond forming process; this is consistent with experimental observations. Moreover, the inherent roles of, and requirement for, two copper ions in this reaction have been elucidated.
AB - Theoretical studies on the chemo- and regioselective. ortho-oxidation reaction of phenols mediated by a biomimetic (μ-η2: 2peroxo)dicopper(II) complex were performed using unrestricted hybrid density functional theory (UB3LYP) calculations, with the aim of providing a guide for the development of new bio-inspired catalysts with the phenolase activity of tyrosinase. Energetic, structural, and electronic analyses suggested the involvement of a side-on (μ-2:2)-Cu 2O2 complex as an active intermediate, and a single electron transfer (SET)-induced electrophilic aromatic substitution mechanism is proposed for the rate-determining C-O bond forming process; this is consistent with experimental observations. Moreover, the inherent roles of, and requirement for, two copper ions in this reaction have been elucidated.
KW - Copper
KW - Oxidation
KW - Peroxo complexes
KW - Phenols
KW - Theoretical calculations
KW - Tyrosinase
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U2 - 10.1002/adsc.200600557
DO - 10.1002/adsc.200600557
M3 - Article
AN - SCOPUS:34547202620
VL - 349
SP - 595
EP - 600
JO - Advanced Synthesis and Catalysis
JF - Advanced Synthesis and Catalysis
SN - 1615-4150
IS - 4-5
ER -