Copper-Catalyzed Monooxygenation of Phenols: Evidence for a Mononuclear Reaction Mechanism

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2022 Mar 28

PMID 35344617

Authors

Rebecca Schneider

Tobias A Engesser

Christian Nather

Ingo Krossing

Felix Tuczek

Affiliations

Soon will be listed here.

Abstract

The Cu salts [Cu(CH CN) ]PF and [Cu(oDFB) ]PF with the very weakly coordinating anion Al(OC(CF ) ) (PF) as well as [Cu(NEt ) ]PF comprising the unique, linear bis-triethylamine complex [Cu(NEt ) ] were synthesized and examined as catalysts for the conversion of monophenols to o-quinones. The activities of these Cu salts towards monooxygenation of 2,4-di-tert-butylphenol (DTBP-H) were compared to those of [Cu(CH CN) ]X salts with "classic" anions (BF , OTf , PF ), revealing an anion effect on the activity of the catalyst and a ligand effect on the reaction rate. The reaction is drastically accelerated by employing Cu -semiquinone complexes as catalysts, indicating that formation of a Cu complex precedes the actual catalytic cycle. This result and other experimental observations show that with these systems the oxygenation of monophenols does not follow a dinuclear, but a mononuclear pathway analogous to that of topaquinone cofactor biosynthesis in amine oxidase.

Citing Articles

Catalytic Ammonia Synthesis Mediated by Molybdenum Complexes with PNP Pincer Ligands: Influence of P/N Substituents and Molecular Mechanism.

Bedbur K, Stucke N, Liehrs L, Krahmer J, Tuczek F Molecules. 2022; 27(22).

PMID: 36431964 PMC: 9692791. DOI: 10.3390/molecules27227843.

Copper-Catalyzed Monooxygenation of Phenols: Evidence for a Mononuclear Reaction Mechanism.

Schneider R, Engesser T, Nather C, Krossing I, Tuczek F Angew Chem Int Ed Engl. 2022; 61(25):e202202562.

PMID: 35344617 PMC: 9323449. DOI: 10.1002/anie.202202562.

References

Engesser T, Friedmann C, Martens A, Kratzert D, Malinowski P, Krossing I . Homoleptic Gold Acetonitrile Complexes with Medium to Very Weakly Coordinating Counterions: Effect on Aurophilicity?. Chemistry. 2016; 22(42):15085-15094. DOI: 10.1002/chem.201602797. View

Decker H, Schweikardt T, Tuczek F . The first crystal structure of tyrosinase: all questions answered?. Angew Chem Int Ed Engl. 2006; 45(28):4546-50. DOI: 10.1002/anie.200601255. View

Krossing I . Ag(P4)2(+): the first homoleptic metal-phosphorus cation. J Am Chem Soc. 2001; 123(19):4603-4. DOI: 10.1021/ja002007m. View

Brazeau B, Johnson B, Wilmot C . Copper-containing amine oxidases. Biogenesis and catalysis; a structural perspective. Arch Biochem Biophys. 2004; 428(1):22-31. DOI: 10.1016/j.abb.2004.03.034. View

Rolff M, Schottenheim J, Peters G, Tuczek F . The first catalytic tyrosinase model system based on a mononuclear copper(I) complex: kinetics and mechanism. Angew Chem Int Ed Engl. 2010; 49(36):6438-42. DOI: 10.1002/anie.201000973. View

Krossing I, van W . Superweak complexes of tetrahedral P4 molecules with the silver cation of weakly coordinating anions. Chemistry. 2002; 8(3):700-11. DOI: 10.1002/1521-3765(20020201)8:3<700::AID-CHEM700>3.0.CO;2-C. View

Liebhauser P, Keisers K, Hoffmann A, Schnappinger T, Sommer I, Thoma A . Record Broken: A Copper Peroxide Complex with Enhanced Stability and Faster Hydroxylation Catalysis. Chemistry. 2017; 23(50):12171-12183. DOI: 10.1002/chem.201700887. View

Matoba Y, Kumagai T, Yamamoto A, Yoshitsu H, Sugiyama M . Crystallographic evidence that the dinuclear copper center of tyrosinase is flexible during catalysis. J Biol Chem. 2006; 281(13):8981-90. DOI: 10.1074/jbc.M509785200. View

Schneider R, Engesser T, Nather C, Krossing I, Tuczek F . Copper-Catalyzed Monooxygenation of Phenols: Evidence for a Mononuclear Reaction Mechanism. Angew Chem Int Ed Engl. 2022; 61(25):e202202562. PMC: 9323449. DOI: 10.1002/anie.202202562. View

10.

Gaule T, Smith M, Tych K, Pirrat P, Trinh C, Pearson A . Oxygen Activation Switch in the Copper Amine Oxidase of Escherichia coli. Biochemistry. 2018; 57(36):5301-5314. PMC: 6136094. DOI: 10.1021/acs.biochem.8b00633. View

11.

Alvarez S . Corrigendum: Coordinating Ability of Anions, Solvents, Amino Acids, and Gases towards Alkaline and Alkaline-Earth Elements, Transition Metals, and Lanthanides. Chemistry. 2020; 26(39):8663. DOI: 10.1002/chem.202001687. View

12.

Elwell C, Gagnon N, Neisen B, Dhar D, Spaeth A, Yee G . Copper-Oxygen Complexes Revisited: Structures, Spectroscopy, and Reactivity. Chem Rev. 2017; 117(3):2059-2107. PMC: 5963733. DOI: 10.1021/acs.chemrev.6b00636. View

13.

Klinman J, Bonnot F . Intrigues and intricacies of the biosynthetic pathways for the enzymatic quinocofactors: PQQ, TTQ, CTQ, TPQ, and LTQ. Chem Rev. 2013; 114(8):4343-65. PMC: 3999297. DOI: 10.1021/cr400475g. View

14.

Askari M, Rodriguez-Solano L, Proppe A, McAllister B, Lumb J, Ottenwaelder X . Catalytic aerobic oxidation of phenols to ortho-quinones with air-stable copper precatalysts. Dalton Trans. 2015; 44(27):12094-7. DOI: 10.1039/c5dt00822k. View

15.

Askari M, Esguerra K, Lumb J, Ottenwaelder X . A Biomimetic Mechanism for the Copper-Catalyzed Aerobic Oxygenation of 4-tert-Butylphenol. Inorg Chem. 2015; 54(17):8665-72. DOI: 10.1021/acs.inorgchem.5b01297. View

16.

Mirica L, Vance M, Jackson Rudd D, Hedman B, Hodgson K, Solomon E . Tyrosinase reactivity in a model complex: an alternative hydroxylation mechanism. Science. 2005; 308(5730):1890-2. DOI: 10.1126/science.1112081. View

17.

DuBois J, Klinman J . Mechanism of post-translational quinone formation in copper amine oxidases and its relationship to the catalytic turnover. Arch Biochem Biophys. 2004; 433(1):255-65. DOI: 10.1016/j.abb.2004.08.036. View

18.

Herres-Pawlis S, Verma P, Haase R, Kang P, Lyons C, Wasinger E . Phenolate hydroxylation in a bis(mu-oxo)dicopper(III) complex: lessons from the guanidine/amine series. J Am Chem Soc. 2009; 131(3):1154-69. PMC: 2663633. DOI: 10.1021/ja807809x. View

19.

Santiso-Quinones G, Higelin A, Schaefer J, Bruckner R, Knapp C, Krossing I . Cu[Al(OR(F))4] starting materials and their application in the preparation of [Cu(S(n))]+ (n=12, 8) complexes. Chemistry. 2009; 15(27):6663-77. DOI: 10.1002/chem.200900244. View

20.

Engesser T, Lichtenthaler M, Schleep M, Krossing I . Reactive p-block cations stabilized by weakly coordinating anions. Chem Soc Rev. 2015; 45(4):789-899. PMC: 4758321. DOI: 10.1039/c5cs00672d. View