Journal Article

FZJ-2020-03835

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Exceptional Substrate Diversity in Oxygenation Reactions Catalyzed by a Bis(μ‐oxo) Copper Complex

Paul, M.RWTH* ; Teubner, M.RWTH* ; Grimm‐Lebsanft, B. ; Golchert, C.RWTH* ; Meiners, Y.RWTH* ; Senft, L. ; Keisers, K.RWTH* ; Liebhäuser, P.RWTH* ; Rösener, T.RWTH* ; Biebl, F. ; Buchenau, S. ; Naumova, M.DESY* ; Murzin, V.DESY* ; Krug, R.FZJ* ; Hoffmann, A.RWTH* ; Pietruszka, J.FZJ* ; Ivanović‐Burmazović, I. ; Rübhausen, M. ; Herres‐Pawlis, S. (Corresponding author)RWTH*

2020
Wiley-VCH Weinheim

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Please use a persistent id in citations: http://hdl.handle.net/2128/25836  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.

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Contributing Institute(s):

1. Institut für Bioorganische Chemie (HHUD) (IBOC)
2. Biotechnologie (IBG-1)

Research Program(s):

1. 581 - Biotechnology (POF3-581) (POF3-581)

Appears in the scientific report 2020

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Database coverage:
; ; ; Chemical Reactions ; Clarivate Analytics Master Journal List ; Current Contents - Physical, Chemical and Earth Sciences ; DEAL Wiley ; Ebsco Academic Search ; Essential Science Indicators ; IF >= 5 ; Index Chemicus ; JCR ; NCBI Molecular Biology Database ; Nationallizenz ; SCOPUS ; Science Citation Index ; Science Citation Index Expanded ; Web of Science Core Collection

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