Exceptional Substrate Diversity in Oxygenation Reactions Catalyzed by a Bis(μ-oxo) Copper Complex
| Autor: | Melissa Teubner, Michael Rübhausen, Melanie Paul, Vadim Murzin, Kristina Keisers, Roxanne Krug, Sonja Herres-Pawlis, Thomas Rösener, Maria Naumova, Christiane Golchert, Jörg Pietruszka, Alexander Hoffmann, Ivana Ivanović-Burmazović, Patricia Liebhäuser, Benjamin Grimm-Lebsanft, Yannick Meiners, Florian Biebl, Laura Senft, Sören Buchenau |
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| Jazyk: | angličtina |
| Rok vydání: | 2020 |
| Předmět: |
Dioxygen Activation
Tyrosinase tyrosinase 010402 general chemistry 01 natural sciences Medicinal chemistry Catalysis chemistry.chemical_compound Guanidine copper catalysis Bicyclic molecule 010405 organic chemistry Ligand Communication Organic Chemistry Substrate (chemistry) phenazines General Chemistry Communications 0104 chemical sciences chemistry ddc:540 Selectivity Fukui function guanidines |
| Zdroj: | Chemistry-a European journal 26(34), 7556-7562 (2020). doi:10.1002/chem.202000664 Chemistry (Weinheim an Der Bergstrasse, Germany) |
| DOI: | 10.18154/rwth-2020-05457 |
| Popis: | Chemistry - a European journal 26(34), 7556-7562 (2020). doi:10.1002/chem.202000664 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 [Cu$_2$($μ$‐O)$_2$(L1)$_2$](X)$_2$ ([O1](X)$_2$, X=PF$_6^−$, BF$_4^−$, OTf$^−$, ClO$_4^−$), 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](PF$_6$)$_2$, 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. Published by Wiley-VCH, Weinheim |
| Databáze: | OpenAIRE |
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