Theoretical study of the hydroxylation of phenolates by the Cu(2)O (2)(N,N'-dimethylethylenediamine) (2) (2+) complex

J Biol Inorg Chem. 2009 Feb;14(2):229-42. doi: 10.1007/s00775-008-0443-y. Epub 2008 Oct 30.

Abstract

Tyrosinase catalyzes the ortho hydroxylation of monophenols and the subsequent oxidation of the diphenolic products to the resulting quinones. In efforts to create biomimetic copper complexes that can oxidize C-H bonds, Stack and coworkers recently reported a synthetic mu-eta(2):eta(2)-peroxodicopper(II)(DBED)(2) complex (DBED is N,N'-di-tert-butylethylenediamine), which rapidly hydroxylates phenolates. A reactive intermediate consistent with a bis-mu-oxo-dicopper(III)-phenolate complex, with the O-O bond fully cleaved, is observed experimentally. Overall, the evidence for sequential O-O bond cleavage and C-O bond formation in this synthetic complex suggests an alternative mechanism to the concerted or late-stage O-O bond scission generally accepted for the phenol hydroxylation reaction performed by tyrosinase. In this work, the reaction mechanism of this peroxodicopper(II) complex was studied with hybrid density functional methods by replacing DBED in the mu-eta(2):eta(2)-peroxodicopper(II)(DBED)(2) complex by N,N'-dimethylethylenediamine ligands to reduce the computational costs. The reaction mechanism obtained is compared with the existing proposals for the catalytic ortho hydroxylation of monophenol and the subsequent oxidation of the diphenolic product to the resulting quinone with the aim of gaining some understanding about the copper-promoted oxidation processes mediated by 2:1 Cu(I)O(2)-derived species.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Catalysis
  • Computer Simulation*
  • Hydroxybenzoates / chemistry*
  • Hydroxybenzoates / metabolism
  • Hydroxylation
  • Models, Chemical*
  • Molecular Structure
  • Monophenol Monooxygenase / metabolism
  • Organometallic Compounds / chemistry*
  • Oxidation-Reduction
  • Quinones / chemical synthesis*
  • Quinones / chemistry
  • Quinones / metabolism
  • Stereoisomerism

Substances

  • Hydroxybenzoates
  • Organometallic Compounds
  • Quinones
  • mu-eta2-eta2-peroxobis(N,N'-dimethylethylenediamine)dicopper(II)
  • Monophenol Monooxygenase
  • phenolic acid