Theoretical studies on ortho-oxidation of phenols with dioxygen mediated by dicopper complex: Hints for a catalyst with the phenolase activity of tyrosinase

Hiroshi Naka, Yoshinori Kondo, Shinya Usui, Yuichi Hashimoto, Masanobu Uchiyama

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8 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)595-600
Number of pages6
JournalAdvanced Synthesis and Catalysis
Volume349
Issue number4-5
DOIs
Publication statusPublished - 2007 Mar 1

Keywords

  • Copper
  • Oxidation
  • Peroxo complexes
  • Phenols
  • Theoretical calculations
  • Tyrosinase

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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