Ruthenium‐Catalyzed Regioselective Direct <i>Ortho</i>‐Acyloxylation of Azoarenes with Carboxylic Acids via C–H Bond Activation

Kianmehr, Ebrahim; Nasab, Sepideh Bahrami

doi:10.1002/ejoc.201801545

Cited by 14 publications

(3 citation statements)

References 68 publications

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“…A ruthenium‐catalysed acyloxylation of azoarenes ( 53 ) with organic acid ( 54 ) was reported by Kianmehr et al [53] . in 2019.…”

Section: Ruthenium‐catalysed C−o Bond Forming Process (Oxygenation)mentioning

confidence: 98%

Recent advances in ruthenium‐catalysed aromatic C−H bond oxygenation, nitrogenation and halogenation

Singh

2024

ChemistrySelect

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The transition metal‐catalysed C−H bond functionalization has emerged as a powerful tool for accessing numerous organic compounds in greener manner with step and atom economy. Remarkable progress has been made in the metal‐catalysed C−H bond functionalization during the past decades and the trend is continuing as new reactions are being added. In the transition metal‐catalysed C−H bond functionalization, a growing attention has been paid on ruthenium, particularly, the stable ruthenium(II) as it allows several C−H bond functionalization reactions to perform in water with high selectivity. The ruthenium‐catalysed C−H bond functionalization reactions, such as arylation, alkenylation, annulation, cyanation, amination and silylation just to mention some have been well documented in numerous published papers, book chapters and review articles. However, as ruthenium‐catalysed C−H functionalization has been growing rapidly, a comprehensive review is necessary from time to time to highlight the progress made in this ever expanding field. In view of this, the manuscript presents the ruthenium‐catalysed direct C−O, C−N and C‐halogen bond forming reactions involving aromatic C−H bond covering oxygenation, amination, amidation, imidation, nitration and halogenation reported from 2012 to 2022.

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“…A ruthenium‐catalysed acyloxylation of azoarenes ( 53 ) with organic acid ( 54 ) was reported by Kianmehr et al [53] . in 2019.…”

Section: Ruthenium‐catalysed C−o Bond Forming Process (Oxygenation)mentioning

confidence: 98%

Recent advances in ruthenium‐catalysed aromatic C−H bond oxygenation, nitrogenation and halogenation

Singh

2024

ChemistrySelect

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“…The results of these reactions included direct ortho ‐acyloxylation of 2‐functional arenes, benzylation with toluene, and cross‐coupling of aromatic compounds via C−H bond activation . An oxidant and heating condition were required, while the Pd(OAc) 2 – was mostly employed as the metal‐catalyst.…”

Section: Nucleophilic Acidsmentioning

confidence: 99%

Arylacetic Acids in Organic Synthesis

et al. 2019

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Arylacetic acids are widely used in organic reactions and their recent advances are summarized in six categories according to their triggered pathways: (1) the acid as directing group in ortho-or meta-CÀ H activation; (2) decarboxylation; (3) deprotonation; (4) nucleophilic methylenes; (5) nucleophilic acids; (6) electrophilic acids. Reactions with alkenes, alkynes, aldehydes, amines, water, Grignard reagents, silanes and so forth are discussed. We hope this Minireview will promote future research in this area. Recently, the Zeng group [3g] reported a weakly coordinationassisted alkynylation of arylacetic acids with iridium catalysis under air atmosphere (Eq. 2-2). It was supported the sixmembered ring cycloiridiated 2.5 acted as the key intermediate. The alkynylation of indole, thiophene, pyrrole, and benzo[b] thiophene afforded better yields than phenylacetic acids. The acid moiety could also participated in the intramolecular ortho-CÀ H activation, which was developed by the Shi group to obtain lactonization 2.6 (Eq. 2-3) (Scheme 2). Meta-CÀ H ArylationThe study of Yu group [3e] in 2017 revealed a successful control of meta selectivity 3.1 of arylation from aryl iodides (Eq. 3-1). The use of mono-protected 3-amino-2-hydroxypyridine (as ligand) and 2-carbomethoxynorbornene (NBE-CO 2 Me) were crucial. In the absence of NBE-CO 2 Me, only ortho-arylated product was obtained. This method was still efficient in a gramsale (Scheme 3). Decarboxylation Decarboxylative CouplingAs shown in Scheme 4, the decarboxylation could generate benzyl radicals 4.1. Then, direct couplings of 4.1 with diverse [ + ] These authors contributed equally. Scheme 1. Six categories based on triggered mechanism. 2 3 4 5 6 7 8 . Passerini Three-Component ReactionThe Passerini reaction was the oldest multicomponent reaction (MCR) [37d] in which isocyanides, carboxylic acids and aldehydes were used. It was powerful for the rapid construction of complex molecules. The tactic to expand the scope of Passerini reaction was to use surrogates of the carbonyl partners. As described in Scheme 51, syn-chlorooximes, [37b] diazoketones, [37c] alcohols, [37d,e] azirines [37f] and isatins [37g] could be employed instead of aryl or alkyl aldehydes [37a] (Scheme 51). Besides, in 2018, Zhang and co-workers [37] have firstly reported asymmetric phosphoric acid-catalyzed four-component Ugi reaction, which Scheme 45. BTM-catalyzed cycloaddition. Scheme 46. HBTM-catalyzed cycloaddition. Scheme 47. TFA-catalyzed reaction. Scheme 48. Friedel-Crafts triggered tandem reactions. Scheme 49. C-acylation of 1,3-diones. Scheme 50. C-acylation of 1,3-indandiones.

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“…Very recently, Kianmehr and Bahrami-Nasab employed standard [{RuCl 2 (p-cymene)} 2 ] catalyst, in combination with K 2 S 2 O 8 and KPF 6 for regioselective ortho-acyloxylation of azoarenes 22 with carboxylic acids 23. 28 These reactions were performed in MeCN at 110 C and afforded the corresponding ortho-acyloxylated azoarene derivatives 24 in moderate to high yields (Scheme 10). Notably, other ruthenium catalysts such as RuCl 2 (PPh 3 ) 2 and RuCl 3 + H 2 O were also found to catalyze this dehydrogenative cross-coupling reaction, albeit at considerably lower efficiencies.…”

Section: Ruthenium-catalyzed Reactionsmentioning

confidence: 99%

Cross-dehydrogenative coupling reactions between arenes (C–H) and carboxylic acids (O–H): a straightforward and environmentally benign access to O-aryl esters

et al. 2019

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Ruthenium‐Catalyzed Regioselective Direct Ortho‐Acyloxylation of Azoarenes with Carboxylic Acids via C–H Bond Activation

Cited by 14 publications

References 68 publications

Recent advances in ruthenium‐catalysed aromatic C−H bond oxygenation, nitrogenation and halogenation

Recent advances in ruthenium‐catalysed aromatic C−H bond oxygenation, nitrogenation and halogenation

Arylacetic Acids in Organic Synthesis

Cross-dehydrogenative coupling reactions between arenes (C–H) and carboxylic acids (O–H): a straightforward and environmentally benign access to O-aryl esters

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