Recent progress in catalytic oxygenation of aromatic C–H groups with the environmentally benign oxidants H2O2 and O2

Ottenbacher, Roman V.; Talsi, Evgenii P.; Bryliakov, Konstantin P.

doi:10.1002/aoc.5900

Cited by 25 publications

(16 citation statements)

References 136 publications

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“…Aromatic compounds have been central to chemistry over the last two decades, and discoveries concerning their properties, [1] their preparation, [2] and their production have impacted society as a whole, from dyes and colorants [3] to drugs [4] and crop protection agents. [5] The chemistry of aromatic compounds fills textbook chapters, [6] and students in many disciplines learn the basic reactivity of these compounds, such as electrophilic or nucleophilic aromatic substitution.…”

Section: Introductionmentioning

confidence: 99%

Nucleophilic Attack on Nitrogen in Tetrazines by Silyl-Enol Ethers

et al. 2021

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The nucleophilic addition to nitrogen in 3-monosubstituted s-tetrazines under mild conditions is reported, by using silyl-enol ethers as the nucleophiles and mediated by BF 3 . The preference for this azaphilic addition over the usually observed inverse electron demand Diels-Alder reactions was determined experimentally and evaluated theoretically. In this regard, the influence of the effect of BF 3 -coordination to s-tetrazines was investigated thoroughly. The substrate dependency of this unusual reaction was rationalized by determination of the activation barriers and on the basis of the activation strain model by employing density functional theory. Lastly, the decomposition of the unstable adducts was examined and an interesting rearrangement to a triazine derived structure was observed.

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Section: Introductionmentioning

confidence: 99%

Nucleophilic Attack on Nitrogen in Tetrazines by Silyl-Enol Ethers

et al. 2021

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“…The primary oxidants including O 3 , H 2 O 2 , O 2 , transition metal oxo-species, light, and electrical energy are employed to remove the organic (and sometimes inorganic) wastes in wastewater via the reactive oxygen species (ROS) and/or UV light (Deng and Zhao, 2015). These remediation processes can also be properly controlled and applied for the selective catalytic oxidation of hydrocarbons by designing variable homo-and heterogeneous catalyst systems to achieve green and environmentally benign fine chemical production (Ottenbacher et al, 2020;Suib et al, 2020).…”

Section: Introductionmentioning

confidence: 99%

Selective Oxidation of Simple Aromatics Catalyzed by Nano-Biomimetic Metal Oxide Catalysts: A Mini Review

et al. 2020

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The process of selective oxy-functionalization of hydrocarbons using peroxide, O 3 , H 2 O 2 , O 2 , and transition metals can be carried out by the reactive oxygen species such as hydroxyl/hydroperoxyl radical and/or metal oxygenated species generated in the catalytic reaction. Thus, a variety of mechanisms have been proposed for the selective catalytic oxidation of various hydrocarbons including light alkanes, olefins, and simple aromatics by the biological metalloproteins and their biomimetics either in their homogeneous or heterogeneous platforms. Most studies involving these metalloproteins are Fe or Cu monooxygenases. The pathways carried out by these metalloenzymes in the oxidation of C-H bonds invoke either radical reaction mechanisms including Fenton's chemistry and hydrogen atom transfer followed by radical rebound reaction mechanism or electrophilic oxygenation/O-atom transfer by metal-oxygen species. In this review, we discuss the metal oxide nano-catalysts obtained from metal salts/molecular precursors (M = Cu, Fe, and V) that can easily form in situ through the oxidation of substrates using H 2 O 2(aq) in CH 3 CN, and be facilely separated from the reaction mixtures as well as recycled for several times with comparable catalytic efficiency for the highly selective conversion from hydrocarbons including aromatics to oxygenates. The mechanistic insights revealed from the oxy-functionalization of simple aromatics mediated by the novel biomimetic metal oxide materials can pave the way toward developing facile, cost-effective, and highly efficient nano-catalysts for the selective partial oxidation of simple aromatics.

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“…For this reaction, the heterogenous and homogeneous catalysts involving transition metals such as vanadium, iron and copper have been extensively investigated. 1–7 Among which, heterogeneous vanadium catalysts have attracted significant attention owing to their higher activity and the convenience of recovery. 8–16 However, like other heterogeneous catalytic systems, the supported vanadium catalysts always suffer from the leaching of vanadium species.…”

Section: Introductionmentioning

confidence: 99%