Aldehyde‐Assisted Ruthenium(II)‐Catalyzed CH Oxygenations

Yang, Fuzi; Rauch, Karsten; Kettelhoit, Katharina; Ackermann, Lutz

doi:10.1002/ange.201405647

Cited by 44 publications

(6 citation statements)

References 54 publications

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“…In 2013, Jiao and co‐workers described a novel PdCl 2 and NHPI co‐catalyzed direct C( sp 2 )–H hydroxylation of 2‐phenylpyridines under neutral conditions with only 2‐(pyridin‐2‐yl)phenol being obtained . In 2014, Ackermann reported the ruthenium‐catalyzed C–H oxygenation with the assistance of weakly coordinating aldehydes . In 2015, Chakraborti developed a Pd‐catalyzed aryl C( sp 2 )–H activation with bioactive and sterically hindered heterocyclic moieties and other acyclic functionalities (azo, amide, anilide, carbamate and urea) as versatile directing groups with Na 2 S 2 O 8 as the oxidant .…”

Section: Methodsmentioning

confidence: 99%

Disulfide‐Directed C–H Hydroxylation for Synthesis of Sulfonyl Diphenyl Sulfides and 2‐(Phenylthio)phenols with Oxygen as Oxidant

et al. 2017

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Section: Methodsmentioning

confidence: 99%

Disulfide‐Directed C–H Hydroxylation for Synthesis of Sulfonyl Diphenyl Sulfides and 2‐(Phenylthio)phenols with Oxygen as Oxidant

et al. 2017

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“…Transition metal catalyzed CÀ H activation reaction of aromatic aldehyde is very limited and challenging because of their excessive tendency to undergo oxidation under the metal catalyzed oxidative reaction salicyldehyde (Scheme 45). [59] The intramolecular and intermolecular kinetic isotope effect (KIE) experiments established the coordination of aldehyde carbonyl with ruthenium catalyst for activation of ortho CÀ H bond.…”

Section: Phi(otfa) 2 Mediated Hydroxylationmentioning

confidence: 99%

“…to obtain best yield of salicyldehyde (Scheme 45). [59] The intramolecular and intermolecular kinetic isotope effect (KIE) experiments established the coordination of aldehyde carbonyl with ruthenium catalyst for activation of ortho C−H bond.…”

Section: Tfa− From Tfa and Phi(otfa)2 As Hydroxylating Agentmentioning

confidence: 99%

Recent Advancements on Transition‐Metal‐Catalyzed, Chelation‐Induced ortho‐Hydroxylation of Arenes

Iqbal

Joshi

2020

Adv Synth Catal

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The phenols are key intermediates as well as desired products in many target oriented syntheses. The conversion of CÀ H bond to CÀ O bond is one of the most challenging tasks in organic synthesis. In last few decades, the hydroxylation of aromatic compounds has drawn a considerable attention because of their importance in Pharmaceutical industry, material chemistry, polymers and in agrochemicals. Indeed, transition-metal-catalyzed, coordination-assisted regio-and chemoselective orthohydroxylation of arenes has become very efficient and popular strategy to obtain good yields of phenols with tolerance of a wide range of functional groups. This review is the comprehensive summary of recent advancement on Pd-, Ru-, Rh-, Cu-and Ir-catalyzed, chelation-controlled regioselective ortho-CÀ H bond hydroxylation of aromatic compounds in the presence of diverse hydroxylating agents. The review has been classified on the sources of hydroxylating agents used in reaction.

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“…17 With the development of transition metal-catalyzed C─hydrogen (H) activation, direct C─H hydroxylation was regarded as one of the efficient avenues for the introduction of the desired functional group on the selected targets. [18][19][20][21][22][23][24][25][26][27][28][29] Therefore, it was considered as a novel strategy to obtain functionalized phenols based on the hydroxylation of inert C─H bonds. In 2010, Pan and co-workers reported that 2-(phenylthio)phenols could be smoothly synthesized from phenols and aromatic halides through C─H functionalization.…”

Section: Introductionmentioning

confidence: 99%

The Cascade C─H functionalization with sequential hydroxylation and oxidation through heterogeneous BINAP‐copper on hydrotalcite

Zhang

Wang

et al. 2020

J of Chemical Tech & Biotech

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BACKGROUND Aromatic thioether derivatives exist widely in natural products and have significant applications in modern synthesis and the pharmaceutical industry; for example, 2‐sulfanylphenols and arylthioquinones are important intermediates in the processing of anticancer, antibiotic, antivirus and antimalarial drugs. Direct C─H hydroxylation was considered as one of the efficient methods for the synthesis of these compounds. Homogeneous transition metal catalysts usually were used through a cross‐coupling of halogen‐substituted phenols with thiophenols. However, from the perspectives of sustainable development and easy recovery, it is necessary to develop an efficient and recoverable catalytic system to realize the synthesis of aromatic thioether derivatives with good efficiency and recyclability. RESULTS The heterogeneous catalyst [Cu(binap)I]2@HT in the present work showed good catalytic activity for the C─H hydroxylation of benzenethiol and phenylboronic acid. The catalytic system was tolerant to various substituents including alkyl, alkoxy, ester, halogen or trifluoromethyl on the phenyl ring of the thiophenols or arylboric acids. In addition to electron‐donating groups, the products with strong electron‐withdrawing groups, such as methyl formylate and trifluoromethyl also were achieved with good yields at 90 °C for 12 h (68% and 66%, respectively). Repeated experiment results showed that the catalyst could be reused at least five times without obvious decrease in catalytic activity. CONCLUSION A BINAP‐Cu complex supported on hydrotalcite was prepared and used as a heterogeneous catalyst for the C─H activation of thiophenol under mild reaction conditions. Through a cascade C─H hydroxylation and further oxidation process, 2‐Sulfanylphenols and arylthioquinones could be obtained with moderate‐to‐good yields for a series of 2‐(phenylthio)phenol derivatives using the heterogeneous catalyst [Cu(binap)I]2@HT. In addition, this heterogeneous catalyst showed good recylbility. © 2020 Society of Chemical Industry

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Aldehyde‐Assisted Ruthenium(II)‐Catalyzed CH Oxygenations

Cited by 44 publications

References 54 publications

Disulfide‐Directed C–H Hydroxylation for Synthesis of Sulfonyl Diphenyl Sulfides and 2‐(Phenylthio)phenols with Oxygen as Oxidant

Disulfide‐Directed C–H Hydroxylation for Synthesis of Sulfonyl Diphenyl Sulfides and 2‐(Phenylthio)phenols with Oxygen as Oxidant

Recent Advancements on Transition‐Metal‐Catalyzed, Chelation‐Induced ortho‐Hydroxylation of Arenes

The Cascade C─H functionalization with sequential hydroxylation and oxidation through heterogeneous BINAP‐copper on hydrotalcite

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