Selective photocatalytic aerobic bromination with hydrogen bromide via an electron-transfer state of 9-mesityl-10-methylacridinium ion

Ohkubo, Kei; Mizushima, Kota; Iwata, Ryosuke; Fukuzumi, Shunichi

doi:10.1039/c0sc00535e

Cited by 190 publications

(177 citation statements)

References 62 publications

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“…352 The regioselectivity of this addition is not specified where nonequivalent sites of Br − addition exist. Yields of methoxyarenes with methyl substituents give significantly lower yields (e.g., 87.4), owing to competitive .…”

Section: -Dicarbonyl Compoundsmentioning

confidence: 99%

Organic Photoredox Catalysis

2016

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In this review, we highlight the use of organic photoredox catalysts in a myriad of synthetic transformations with a range of applications. This overview is arranged by catalyst class where the photophysics and electrochemical characteristics of each is discussed to underscore the differences and advantages to each type of single electron redox agent. We highlight both net reductive and oxidative as well as redox neutral transformations that can be accomplished using purely organic photoredox-active catalysts. An overview of the basic photophysics and electron transfer theory is presented in order to provide a comprehensive guide for employing this class of catalysts in photoredox manifolds.

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Section: -Dicarbonyl Compoundsmentioning

confidence: 99%

Organic Photoredox Catalysis

2016

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“…Studies by Fukuzumi 12 and Yoshida 20 have demonstrated the utility of computational methods to explain the regioselectivity for a few selected examples of aryl bromination and amination reactions, respectively, that proceed via cation radicals. However, both of these reports focused on simple benzenoid substrates.…”

Section: Introductionmentioning

confidence: 99%

Predictive Model for Site-Selective Aryl and Heteroaryl C–H Functionalization via Organic Photoredox Catalysis

Margrey

McManus

Bonazzi³

et al. 2017

J. Am. Chem. Soc.

152

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Direct C–H functionalization of aromatic compounds is a useful synthetic strategy that has garnered much attention because of its application to pharmaceuticals, agrochemicals, and late-stage functionalization reactions on complex molecules. On the basis of previous methods disclosed by our lab, we sought to develop a predictive model for site selectivity and extend this aryl functionalization chemistry to a selected set of heteroaromatic systems commonly used in the pharmaceutical industry. Using electron density calculations, we were able to predict the site selectivity of direct C–H functionalization in a number of heterocycles and identify general trends observed across heterocycle classes.

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“…15,16 Bromination of various aromatic compounds has also been achieved without using toxic bromine. 17 The donor–acceptor linked dyad can be also utilized in the oxygenation of aromatic compounds to produce aromatic aldehydes, 18 which is a key chemical reaction for the production of precursors of a variety of fine or speciality chemicals such as pharmaceutics, organic dyes, pesticides and perfumes. 19–24 …”

Section: Introductionmentioning

confidence: 99%

Improvement of durability of an organic photocatalyst in p-xylene oxygenation by addition of a Cu(ii) complex

Yamada

Maeda

Ohkubo

et al. 2012

Phys. Chem. Chem. Phys.

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The catalytic durability of an organic photocatalyst, 9-mesityl-10-methyl acridinium ion (Acr+–Mes), has been dramatically improved by the addition of [{tris(2-pyridylmethyl)amine}-CuII](ClO4)2 ([(tmpa)CuII]2+) in the photocatalytic oxygenation of p-xylene by molecular oxygen in acetonitrile. Such an improvement is not observed by the addition of Cu(ClO4)2 in the absence of organic ligands. The addition of [(tmpa)Cu]2+ in the reaction solution resulted in more than an 11 times higher turnover number (TON) compared with the TON obtained without [(tmpa)CuII]2+. In the photocatalytic oxygenation, a stoichiometric amount of H2O2 formation was observed in the absence of [(tmpa)CuII]2+, however, much less H2O2 formation was observed in the presence of [(tmpa)CuII]2+. The photocatalytic mechanism was investigated by laser flash photolysis measurements in order to detect intermediates. The reaction of O2˙− with [(tmpa)CuII]2+ monitored by UV-vis spectroscopy in propionitrile at 203 K suggested formation of [{(tmpa)CuII}2O2]2+, a transformation which is crucial for the overall 4-electron reduction of molecular O2 to water, and a key in the observed improvement in the catalytic durability of Acr+–Mes.

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Selective photocatalytic aerobic bromination with hydrogen bromide via an electron-transfer state of 9-mesityl-10-methylacridinium ion

Cited by 190 publications

References 62 publications

Organic Photoredox Catalysis

Organic Photoredox Catalysis

Predictive Model for Site-Selective Aryl and Heteroaryl C–H Functionalization via Organic Photoredox Catalysis

Improvement of durability of an organic photocatalyst in p-xylene oxygenation by addition of a Cu(ii) complex

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