<i>N</i>-Hydroxybenzimidazole as a structurally modifiable platform for<i>N</i>-oxyl radicals for direct C–H functionalization reactions

Yoshii, Tomomi; Tsuzuki, Shigeyuki; Sakurai, S.; Sakamoto, Ryu; Jiang, Julong; Hatanaka, Miho; Matsumoto, Akira; Maruoka, Keiji

doi:10.1039/d0sc02134b

Cited by 28 publications

(13 citation statements)

References 88 publications

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“…In the presence of a catalytic amount of NHBI, the aldehydic C− H bond was directly converted into a C−F bond using 311G(d,p) level of theory in SMD (MeCN). 66 The calculated BDE of the reference compound (NHPI) was 77.6 kcal/mol.…”

Section: Nhpi Analogues Basedmentioning

confidence: 98%

“… a The O–H BDE (kcal/mol) was calculated at the B3LYP-D3/6-311G(d,p) level of theory in SMD (MeCN) . The calculated BDE of the reference compound (NHPI) was 77.6 kcal/mol. …”

Section: Achiral N-hydroxy Catalystsmentioning

confidence: 99%

“…In 2020, Maruoka and co-workers designed a novel class of catalysts based on NHBI and explored their potential to generate the corresponding N-oxyl radicals for C−H functionalization (Scheme 26). 66 In order to evaluate the catalytic activities of NHBI derivatives, Maruoka and co-workers applied these catalysts to the benzylic C−H amination of ethylbenzene as a model reaction. The structures were flexibly modified, allowing facile tuning of their catalytic performance.…”

Section: Nhpi Analogues Basedmentioning

confidence: 99%

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Development of N-Hydroxy Catalysts for C–H Functionalization via Hydrogen Atom Transfer: Challenges and Opportunities

Luan

2022

ACS Catal.

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C–H functionalization via hydrogen atom transfer is an attractive method of decorating inert C–H bonds, yet it remains challenging so far. In such a reaction, the hydrogen abstractor generally plays a crucial role in determining the reactivity and selectivity. Among the various hydrogen abstractors developed, N-hydroxyphthalimide (NHPI) bearing an N-hydroxy group and two adjacent carbonyl groups has features including easy preparation, convenient modification, and a superior catalytic ability in many reactions. A large variety of electron-deficient N-hydroxy catalysts based on NHPI, including NHPI derivatives and analogues, have been successively developed and applied in a broad range of C–H functionalization reactions. This review comprehensively summarizes the development of N-hydroxy catalysts, with a special focus on the relationship between structure and performance.

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Section: Nhpi Analogues Basedmentioning

confidence: 98%

“… a The O–H BDE (kcal/mol) was calculated at the B3LYP-D3/6-311G(d,p) level of theory in SMD (MeCN) . The calculated BDE of the reference compound (NHPI) was 77.6 kcal/mol. …”

Section: Achiral N-hydroxy Catalystsmentioning

confidence: 99%

Section: Nhpi Analogues Basedmentioning

confidence: 99%

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Development of N-Hydroxy Catalysts for C–H Functionalization via Hydrogen Atom Transfer: Challenges and Opportunities

Luan

2022

ACS Catal.

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“…Unfortunately, it is not easy to modify the structure of N-hydroxyimides. A step forward in the development of N-oxyl-catalyzed transformations was made with the introduction of a new catalyst type, N-hydroxybenzimidazoles [84]. The N-hydroxybenzimidazole core has several modification sites that allow one to control the properties of the catalyst over a wide range.…”

Section: N-oxyl Radical Catalysismentioning

confidence: 99%

Redox-active molecules as organocatalysts for selective oxidative transformations – an unperceived organocatalysis field

Lopat’eva¹,

Krylov²,

Lapshin³

et al. 2022

Beilstein J. Org. Chem.

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Organocatalysis is widely recognized as a key synthetic methodology in organic chemistry. It allows chemists to avoid the use of precious and (or) toxic metals by taking advantage of the catalytic activity of small and synthetically available molecules. Today, the term organocatalysis is mainly associated with redox-neutral asymmetric catalysis of C–C bond-forming processes, such as aldol reactions, Michael reactions, cycloaddition reactions, etc. Organophotoredox catalysis has emerged recently as another important catalysis type which has gained much attention and has been quite well-reviewed. At the same time, there are a significant number of other processes, especially oxidative, catalyzed by redox-active organic molecules in the ground state (without light excitation). Unfortunately, many of such processes are not associated in the literature with the organocatalysis field and thus many achievements are not fully consolidated and systematized. The present article is aimed at overviewing the current state-of-art and perspectives of oxidative organocatalysis by redox-active molecules with the emphasis on challenging chemo-, regio- and stereoselective CH-functionalization processes. The catalytic systems based on N-oxyl radicals, amines, thiols, oxaziridines, ketone/peroxide, quinones, and iodine(I/III) compounds are the most developed catalyst types which are covered here.

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“…Therefore, only limited numbers of reports on the transformation of branched aldehydes have been reported so far. Apparently, the key to minimize the decarbonylation of branched acyl radicals lies in an appropriate choice of radical catalyst/reagent, which can effectively activate the C(O)−H bond under mild reaction conditions [4] . In this context, we are interested in the possibility on the catalytic use of hypervalent iodine(III) reagents, which easily undergo photodecomposition by weak UV light or visible light to furnish iodanyl and carboxyl radicals, for the smooth generation of acyl radicals.…”

Section: C−h Bond Activation Of Branched Aldehydes By the Catalytic Use Of Hypervalent Iodine(iii) Reagentsmentioning

confidence: 99%

Development of New Radical‐Mediated Selective Reactions Promoted by Hypervalent Iodine(III) Reagents

Matsumoto

Lee

Maruoka

2020

The Chemical Record

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In this account, we describe our recent developments on the four‐types of hypervalent iodine(III)‐mediated radical reactions in organic synthesis. Firstly, the activation of aldehydic C−H bonds can be successfully effected with hypervalent iodine(III) reagents, thereby allowing the synthesis of various ketones with high efficiency. Secondly, the site‐selective oxidation of unactivated C(sp3)−H bonds of hydrocarbon substrates was realized with designer hypervalent iodine(III) reagents. Thirdly, various perfluoroalkyl and α‐aminoalkyl radicals can be generated from sodium perfluoroalkanesulfinates and sodium α‐aminoalkanesulfinates, respectively, under the influence of hypervalent iodine(III) reagents. Finally, the efficient generation of difluoromethyl radical from hypervalent difluoroacetoxyliodine(III) reagent was realized by photolysis. These four different strategies are illustrated by using various selective radical approaches.

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N-Hydroxybenzimidazole as a structurally modifiable platform forN-oxyl radicals for direct C–H functionalization reactions

Abstract: A novel class of N-oxy radicals based on flexibly modifiable N-hydroxybenzimidazole skeleton was designed and applied to C–H functionalization reactions.

Cited by 28 publications

References 88 publications

Development of N-Hydroxy Catalysts for C–H Functionalization via Hydrogen Atom Transfer: Challenges and Opportunities

Development of N-Hydroxy Catalysts for C–H Functionalization via Hydrogen Atom Transfer: Challenges and Opportunities

Redox-active molecules as organocatalysts for selective oxidative transformations – an unperceived organocatalysis field

Development of New Radical‐Mediated Selective Reactions Promoted by Hypervalent Iodine(III) Reagents

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