Reactions of a Copper(II) Superoxo Complex Lead to C-H and O-H Substrate Oxygenation: Modeling Copper-Monooxygenase C-H Hydroxylation Reaction of a Copper-Dioxygen Complex With Nitrogen Monoxide (·NO) Leads to a Copper(II)-Peroxynitrite Species

摘要

Copper monooxygenase enzymes, including peptidylglycine-α-hydroxylat-ing monooxygenase (PHM) and dopamine β-monooxygenase (DβM), utilize a dinuclear copper unit to catalyze C-H bond activation. The copper site in DβM catalyzes the transformation of dopamine to norepinephrine (Eq. 1) by insertion of an oxygen atom into the benzylic position of the eth-ylamine side chain of dopamine utilizing two-electron oxidation of ascorbic acid. In the case of PHM, this copper enzyme catalyzes the transformation of C-terminal glycine-extended peptides to their α-hydroxylated products (Eq. 2) also using ascorbic acid as the electron donor.