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Keywords:

  • bioinorganic chemistry;
  • enzymes;
  • type 2 monooxygenases;
  • type 3 copper proteins;
  • tyrosinase
Thumbnail image of graphical abstract

Radicals in directed pathways: The μ-η22 peroxo CuII2 intermediate 1 shows a much faster benzylic ligand hydroxylation than systems without phenol. This novel reactivity can be further accelerated by addition of external H-atom donors such as TEMPO-H. The results imply initial H-atom transfer leading to the formation of phenoxyl radicals. A highly reactive copper oxyl intermediate is then formed, which inserts oxygen into the benzylic C[BOND]H bond.