Exceptional Substrate Diversity in Oxygenation Reactions Catalyzed by a Bis(μ-oxo) Copper Complex

Paul M, Teubner M, Grimm-Lebsanft B, Golchert C, Meiners Y, Senft L, Keisers K, Liebhaeuser P, Roesener T, Biebl F, Buchenau S, Naumova M, Murzin V, Krug R, Hoffmann A, Pietruszka J, Ivanovic-Burmazovic I, Ruebhausen M, Herres-Pawlis S (2020)

Publication Type: Journal article

Publication year: 2020

Journal

Chemistry - A European Journal Wiley

DOI: 10.1002/chem.202000664

Abstract

The enzyme tyrosinase contains a reactive side-on peroxo dicopper(II) center as catalytically active species in C−H oxygenation reactions. The tyrosinase activity of the isomeric bis(μ-oxo) dicopper(III) form has been discussed controversially. The synthesis of bis(μ-oxo) dicopper(III) species [Cu2(μ-O)2(L1)2](X)2 ([O1](X)2, X=PF6 − , BF4 −, OTf−, ClO4 −), stabilized by the new hybrid guanidine ligand 2-{2-((dimethylamino)methyl)phenyl}-1,1,3,3-tetramethylguanidine (L1), and its characterization by UV/Vis, Raman, and XAS spectroscopy, as well as cryo-UHR-ESI mass spectrometry, is described. We highlight selective oxygenation of a plethora of phenolic substrates mediated by [O1](PF6)2, which results in mono- and bicyclic quinones and provides an attractive strategy for designing new phenazines. The selectivity is predicted by using the Fukui function, which is hereby introduced into tyrosinase model chemistry. Our bioinspired catalysis harnesses molecular dioxygen for organic transformations and achieves a substrate diversity reaching far beyond the scope of the enzyme.

Authors with CRIS profile

Laura Senft Lehrstuhl für Bioanorganische Chemie Ivana Ivanovic-Burmazovic Lehrstuhl für Bioanorganische Chemie

Involved external institutions

Rheinisch-Westfälische Technische Hochschule (RWTH) Aachen DE Germany (DE) Universität Hamburg (UHH) DE Germany (DE) Deutsches Elektronen-Synchrotron DESY DE Germany (DE) Heinrich-Heine-Universität Düsseldorf DE Germany (DE)

How to cite

APA:

Paul, M., Teubner, M., Grimm-Lebsanft, B., Golchert, C., Meiners, Y., Senft, L.,... Herres-Pawlis, S. (2020). Exceptional Substrate Diversity in Oxygenation Reactions Catalyzed by a Bis(μ-oxo) Copper Complex. Chemistry - A European Journal. https://doi.org/10.1002/chem.202000664

MLA:

Paul, Melanie, et al. "Exceptional Substrate Diversity in Oxygenation Reactions Catalyzed by a Bis(μ-oxo) Copper Complex." Chemistry - A European Journal (2020).

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