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Frontiers of Green Catalytic Selective Oxidations pp 253–276Cite as

Direct C–H Oxidation of Aromatic Substrates in the Presence of Biomimetic Iron Complexes

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Part of the book series: Green Chemistry and Sustainable Technology ((GCST))

Abstract

This chapter is dedicated to one of the most challenging areas of oxidation catalysis—direct oxidation of aromatic C–H groups. The development of environmentally friendly catalyst systems for the direct hydroxylation of aromatic hydrocarbons is an important task of modern catalysis. Biomimetic approach, based on the functional modeling of enzymes by iron complexes of a relatively simple structure, is considered as a promising approach for designing catalyst systems for direct aromatic hydroxylation, relying on nontoxic hydrogen peroxide used as the oxidant. The mechanism of catalytic performance of biomimetic systems is a question of primary importance; deep insight into this issue can both substantially rationalize the development of novel practical catalyst systems for the direct oxidation of aromatic hydrocarbons and enrich our knowledge on the mechanisms of natural metalloenzyme-mediated oxidations. In this chapter, the state-of-the-art in this area is provided, with the mechanistic part based mostly on the authors’ own works.

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Abbreviations

CHP:

Cumene hydroperoxide

EHA:

2-Ethylhexanoic acid

DFT:

Density functional theory

EPR:

Electron paramagnetic resonance

GC:

Gas chromatography

IBA:

Isobutyric acid

IVA:

Isovaleric acid

Me3HQ:

2,3,5-Trimethylhydroquinone

NHC:

N-heterocyclic carbene(s) ligand

PDP:

N,N′-bis(2-pyridylmethyl)-(S,S)-2,2′-bipyrrolidine ligand

PhSH:

Thioanisole

TPA:

Tris(2-pyridylmethyl)amine ligand

TOF:

Turnover frequency of the catalyst

TN:

Turnover number of the catalyst

UV-Vis:

Ultraviolet-visible spectroscopy

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Acknowledgements

Lyakin O.Y. thanks the Russian Foundation for Basic Research, project 18-33-20078, for financial support.

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Authors and Affiliations

  1. Boreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk, 630090, Russia

    Oleg Y. Lyakin & Evgenii P. Talsi

  2. Novosibirsk State University, Pirogova 2, Novosibirsk, 630090, Russia

    Oleg Y. Lyakin & Evgenii P. Talsi

Authors
  1. Oleg Y. Lyakin
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  2. Evgenii P. Talsi
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Correspondence to Oleg Y. Lyakin .

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Editors and Affiliations

  1. Russian Academy of Sciences, Boreskov Institute of Catalysis, Novosibirsk, Russia

    Konstantin P. Bryliakov

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Lyakin, O.Y., Talsi, E.P. (2019). Direct C–H Oxidation of Aromatic Substrates in the Presence of Biomimetic Iron Complexes. In: Bryliakov, K. (eds) Frontiers of Green Catalytic Selective Oxidations. Green Chemistry and Sustainable Technology. Springer, Singapore. https://doi.org/10.1007/978-981-32-9751-7_10

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