Work

A Mononuclear Scenario for the Copper‐Catalyzed Monooxygenation of Phenolic Substrates

Year: 2026

Type: article

Abstract: ABSTRACT Whereas a dinuclear pathway applies to the monooxygenation of phenols by the type 3 copper enzyme tyrosinase, a mononuclear pathway has been identified for the same reaction in corresponding small‐molecule systems. DFT calculations of five copper model complexes reveal that the latter mechanism is energetically feasible, identifying all intermediates, and transition states. The mechanism closely resembles the biosynthesis of the topaquinone (TPQ) cofactor in the enzyme amine oxidase (AO), though the latter process is not catalytic. Additionally, it is shown that the hydroxo‐quinone complex formed after the hydroxylation step further converts into a copper‐geminal diolate species, which is confirmed by MS/MS experiments using isotope labeling with 18 O 2 .

Source: Chemistry - A European Journal

DOI: 10.1002/chem.202503505

Authors: Alexander Koch, Antony Memboeuf, Felix Tuczek, Tobias A. Engesser

Institutions: Christian-Albrechts-Universität zu Kiel, Centre National de la Recherche Scientifique, Laboratoire Chimie Electrochimie Moléculaires et Chimie Analytique

Language: English

Topic: Metal-Catalyzed Oxygenation Mechanisms

Subfield: Inorganic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,640

Funder: Agence Nationale de la Recherche