Bioorganic chemistry

Cu(II)-mediated phenol oxygenation: chemical evidence implicates a unique role of the enzyme active site in promoting the chemically difficult tyrosine monooxygenation in TPQ cofactor biogenesis of copper amine oxidases.

PMID 25676362


Cu(II)-mediated autoxidations of 4-tert-butylphenol under various conditions was studied, the data confirmed imidazole is the best ligand to promote phenol oxygenation. The same reaction of 2,4-di-tert-butylphenol proceeded much more quickly to lead nearly exclusively to oxidative coupling rather than oxygenation under high pressure O2. These results suggested that Cu(II)-catalyzed phenol autoxidation by activating O2 and phenol in terms of a phenoxy radical (ArO)-Cu(II)-superoxide ternary complex, whereas selectivity between oxygenation and coupling depends mainly on the electronic structure of ArO. It is appeared that CuAOs could achieve stoichiometric tyrosine monooxygenation by modulating the redox potential of Cu(II) and stabilizing the ternary complex through protein conformational adjustment.