Theoretical Studies on ortho-Oxidation of Phenols with Dioxygen Mediated by Dicopper Complex: Hints for a Catalyst with the Phenolase Activity of Tyrosinase
✍ Scribed by Hiroshi Naka; Yoshinori Kondo; Shinya Usui; Yuichi Hashimoto; Masanobu Uchiyama
- Publisher
- John Wiley and Sons
- Year
- 2007
- Tongue
- English
- Weight
- 315 KB
- Volume
- 349
- Category
- Article
- ISSN
- 1615-4150
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✦ Synopsis
Abstract
Theoretical studies on the chemo‐ and regioselective ortho‐oxidation reaction of phenols mediated by a biomimetic (μ–η^2^:η^2^peroxo)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–η^2^:η^2^)‐Cu~2~O~2~ complex as an active intermediate, and a single electron transfer (SET)‐induced electrophilic aromatic substitution mechanism is proposed for the rate‐determining CO 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.