A Competing, Dual Mechanism for Catalytic Direct Benzene Hydroxylation from Combined Experimental-DFT Studies

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2018 Apr 6

PMID 29619184

Citations 7

Authors

Laia Vilella

Ana Conde

David Balcells

M Mar Diaz-Requejo

Agusti Lledos

Pedro J Perez

Affiliations

Soon will be listed here.

Abstract

A dual mechanism for direct benzene catalytic hydroxylation is described. Experimental studies and DFT calculations have provided a mechanistic explanation for the acid-free, Tp Cu-catalyzed hydroxylation of benzene with hydrogen peroxide (Tp = hydrotrispyrazolylborate ligand). In contrast with other catalytic systems that promote this transformation through Fenton-like pathways, this system operates through a copper-oxyl intermediate that may interact with the arene ring following two different, competitive routes: (a) electrophilic aromatic substitution, with the copper-oxyl species acting as the formal electrophile, and (b) the so-called rebound mechanism, in which the hydrogen is abstracted by the Cu-O moiety prior to the C-O bond formation. Both pathways contribute to the global transformation albeit to different extents, the electrophilic substitution route seeming to be largely favoured.

Citing Articles

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References

Morimoto Y, Bunno S, Fujieda N, Sugimoto H, Itoh S . Direct hydroxylation of benzene to phenol using hydrogen peroxide catalyzed by nickel complexes supported by pyridylalkylamine ligands. J Am Chem Soc. 2015; 137(18):5867-70. DOI: 10.1021/jacs.5b01814. View

Bianchi D, Bortolo R, Tassinari R, Ricci M, Vignola R . A Novel Iron-Based Catalyst for the Biphasic Oxidation of Benzene to Phenol with Hydrogen Peroxide. Angew Chem Int Ed Engl. 2018; 39(23):4321-4323. DOI: 10.1002/1521-3773(20001201)39:23<4321::AID-ANIE4321>3.0.CO;2-5. View

Gagnon N, Tolman W . [CuO](+) and [CuOH](2+) complexes: intermediates in oxidation catalysis?. Acc Chem Res. 2015; 48(7):2126-31. PMC: 4856291. DOI: 10.1021/acs.accounts.5b00169. View

Conde A, Vilella L, Balcells D, Diaz-Requejo M, Lledos A, Perez P . Introducing copper as catalyst for oxidative alkane dehydrogenation. J Am Chem Soc. 2013; 135(10):3887-96. DOI: 10.1021/ja310866k. View

Huber S, Ertem M, Aquilante F, Gagliardi L, Tolman W, Cramer C . Generating Cu(II)-oxyl/Cu(III)-oxo species from Cu(I)-alpha-ketocarboxylate complexes and O2: in silico studies on ligand effects and C-H-activation reactivity. Chemistry. 2009; 15(19):4886-95. PMC: 2878202. DOI: 10.1002/chem.200802338. View

Balcells D, Raynaud C, Crabtree R, Eisenstein O . The rebound mechanism in catalytic C-H oxidation by MnO(tpp)Cl from DFT studies: electronic nature of the active species. Chem Commun (Camb). 2008; (6):744-6. DOI: 10.1039/b715939k. View

Shilov A, Shulpin G . Activation of Cminus signH Bonds by Metal Complexes. Chem Rev. 2002; 97(8):2879-2932. DOI: 10.1021/cr9411886. View

Conde A, Diaz-Requejo M, Perez P . Direct, copper-catalyzed oxidation of aromatic C-H bonds with hydrogen peroxide under acid-free conditions. Chem Commun (Camb). 2011; 47(28):8154-6. DOI: 10.1039/c1cc12804c. View

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

10.

Eswaramoorthy M, Nair J, Raj A, Itoh N, Shoji H, Namba T . A one-step conversion of benzene to phenol with a palladium membrane. Science. 2002; 295(5552):105-7. DOI: 10.1126/science.1066527. View

11.

Mairena M, Urbano J, Carbajo J, Maraver J, Alvarez E, Diaz-Requejo M . Effects of the substituents in the TpxCu activation of dioxygen: an experimental study. Inorg Chem. 2007; 46(18):7428-35. DOI: 10.1021/ic7007073. View

12.

Span E, Suess D, Deller M, Britt R, Marletta M . The Role of the Secondary Coordination Sphere in a Fungal Polysaccharide Monooxygenase. ACS Chem Biol. 2017; 12(4):1095-1103. PMC: 5554615. DOI: 10.1021/acschembio.7b00016. View

13.

de Visser S, Oh K, Han A, Nam W . Combined experimental and theoretical study on aromatic hydroxylation by mononuclear nonheme iron(IV)-oxo complexes. Inorg Chem. 2007; 46(11):4632-41. DOI: 10.1021/ic700462h. View

14.

Solomon E, Heppner D, Johnston E, Ginsbach J, Cirera J, Qayyum M . Copper active sites in biology. Chem Rev. 2014; 114(7):3659-853. PMC: 4040215. DOI: 10.1021/cr400327t. View

15.

Lundberg M, Blomberg M, Siegbahn P . Oxyl radical required for o-o bond formation in synthetic Mn-catalyst. Inorg Chem. 2004; 43(1):264-74. DOI: 10.1021/ic0348188. View

16.

Bellarosa L, Diez J, Gimeno J, Lledos A, Suarez F, Ujaque G . Highly efficient redox isomerisation of allylic alcohols catalysed by pyrazole-based ruthenium(IV) complexes in water: mechanisms of bifunctional catalysis in water. Chemistry. 2012; 18(25):7749-65. DOI: 10.1002/chem.201103374. View

17.

Yoshizawa K, Kihara N, Kamachi T, Shiota Y . Catalytic mechanism of dopamine beta-monooxygenase mediated by Cu(III)-oxo. Inorg Chem. 2006; 45(7):3034-41. DOI: 10.1021/ic0521168. View

18.

Kunishita A, Scanlon J, Ishimaru H, Honda K, Ogura T, Suzuki M . Reactions of copper(II)-H2O2 adducts supported by tridentate bis(2-pyridylmethyl)amine ligands: sensitivity to solvent and variations in ligand substitution. Inorg Chem. 2008; 47(18):8222-32. DOI: 10.1021/ic800845h. View

19.

Tani M, Sakamoto T, Mita S, Sakaguchi S, Ishii Y . Hydroxylation of benzene to phenol under air and carbon monoxide catalyzed by molybdovanadophosphoric acid. Angew Chem Int Ed Engl. 2005; 44(17):2586-8. DOI: 10.1002/anie.200462769. View

20.

Yamada M, Karlin K, Fukuzumi S . One-Step Selective Hydroxylation of Benzene to Phenol with Hydrogen Peroxide Catalysed by Copper Complexes Incorporated into Mesoporous Silica-Alumina. Chem Sci. 2016; 7(4):2856-2863. PMC: 4951108. DOI: 10.1039/C5SC04312C. View