Nickel-catalyzed oxidative hydroxylation of arylboronic acid: Ni(HBTC)BPY MOF as an efficient and ligand-free catalyst to access phenolic motifs

Latha, Ganesapandian; Devarajan, Nainamalai; Karthik, Murugan; Suresh, Palaniswamy

doi:10.1016/j.catcom.2019.105911

Cited by 17 publications

(8 citation statements)

References 35 publications

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“…As phenols are renowned versatile reaction intermediates in the synthesis of a diverse range of pharmaceutically and industrially important compounds. [33,75] Primarily, reaction conditions were optimized using phenylboronic acid as model substrate and varying the other reaction factors such as solvents, oxidizing agents, time and catalyst loading to get the better yield, and their results are summarized in Table 2. Among the screened solvents and oxidizing agents, H 2 O and CH 3 CN were found to be the best solvent and hydrogen peroxide (H 2 O 2 ) was determined to be an appropriate oxidizing agent (Entries 3 and 7) as in these conditions 99% yield was obtained only in 15 min with both catalyst 1 and 2.…”

Section: Structural Description Of [{Zn(l)(dmf) 4 } • 2bf 4 ]mentioning

confidence: 99%

“…A plausible mechanism for the Zn-CP 1 (representative one) catalysed ipso-hydroxylation of arylboronic acids is described in Scheme 1, based on the literature report. [76,77] [33] Moreover, intermediate (IV) accomplished (I) after eliminating water and re-addition of DMF solvent molecule to Zn-centre of CP. Thereby, catalyst regains its framework architecture and is set for the next cycle of hydroxylation.…”

Section: Structural Description Of [{Zn(l)(dmf) 4 } • 2bf 4 ]mentioning

confidence: 99%

“…[29][30][31] Among all the adapted protocols, CPs/MOFs catalysed ipso-hydroxylation of arylboronic acids in presence of stoichiometric amounts of oxidizing agent has become more attractive because of its high stability, low toxicity, recyclability and cost-effectiveness. [32,33] In addition, the collective presence of Lewis acidic and basic sites in a single CP/MOF along with their luminescent nature provide an extra advantage to the concerned CPs/MOFs to behave as a true multifunctional materials and consequently, can be used for diverse range of applications. [34][35][36] Based on the aforementioned discussion, in the present investigation, we have synthesized two new CPs with formulas [{Zn(L)(DMF) 4 } • 2BF 4 ] α (1) and [{Cd(L) 2 (Cl) 2 } • 2H 2 O] α (2) using ligand L (Ref.…”

Section: Introductionmentioning

confidence: 99%

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Coordination Polymers as a Functional Material for the Selective Molecular Recognition of Nitroaromatics and ipso‐Hydroxylation of Arylboronic Acids

Kumar

Rani

Husain

et al. 2021

Chemistry An Asian Journal

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We report the synthesis and structural characterization of two coordination polymers (CPs), namely; [{Zn-(L) 6 -di(pyridin-4-yl)naphthalene-2,6-dicarboxamide). Crystal packing of 1 reveals the existence of channels running along the b-and c-axis filled by the ligated DMF and lattice anions, respectively. Whereas, crystal packing of 2 reveals that the metallacycles of each 1D chain are intercalating into the groove of adjacent metallacycles resulting in the stacking of 1D loop-chains to form a sheet-like architecture. In addition, both 1 and 2 were exploited as multifunctional materials for the detection of nitroaromatic compounds (NACs) as well as a catalyst in the ipso-hydroxylation of aryl/heteroarylboronic acids. Remarkably, 1 and 2 showed high fluorescence stability in an aqueous medium and displayed a maximum 88% and 97% quenching efficiency for 4-NPH, respectively among all the investigated NACs. The mechanistic investigation of NACs recognition suggested that the fluorescence quenching occurred via electron as well as energy transfer process. Furthermore, the ipso-hydroxylation of aryl/heteroarylboronic acids in presence of 1 and 2 gave up to 99% desired product yield within 15 min in our established protocol. In both cases, 1 and 2 are recyclable upto five cycles without any significant loss in their efficiency.

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Section: Structural Description Of [{Zn(l)(dmf) 4 } • 2bf 4 ]mentioning

confidence: 99%

Section: Structural Description Of [{Zn(l)(dmf) 4 } • 2bf 4 ]mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Coordination Polymers as a Functional Material for the Selective Molecular Recognition of Nitroaromatics and ipso‐Hydroxylation of Arylboronic Acids

Kumar

Rani

Husain

et al. 2021

Chemistry An Asian Journal

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“…In the catalytic hydrogenation reaction, these coordinated unsaturated metal sites can serve as active sites or introduce other metal nanoparticles as catalytic active sites. Introduced other metal nanoparticles, such as palladium, − platinum, − iridium, − nickel, − rhodium, − ruthenium, − silver, − gold, − and MOFs coordinate unsaturated metal sites in the framework through a synergistic effect to jointly improve catalytic performance. Dehydration, cracking, deoxygenation, and other steps can occur during the catalytic hydrogenation reaction.…”

Section: Main Characteristics and Rational Design Of Mof Materials As...mentioning

confidence: 99%

Application of Metal–Organic Framework Materials and Derived Porous Carbon Materials in Catalytic Hydrogenation

Shen

et al. 2020

ACS Sustainable Chem. Eng.

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In the past few decades, metal–organic frameworks (MOFs) have gradually become attractive materials in various fields due to their unique properties (adjustable pore size, large specific surface area, highly ordered structure, uniformly distributed metal nodes, good modifiability). MOF-derived porous carbon materials have also attracted great interest in many application fields due to their adjustable chemical and physical properties. The hydrogenation reaction is an important type of reaction in the chemical industry. The catalysts play an important role in the hydrogenation reaction. In recent years, MOFs and derived porous carbon materials have had extensive application in catalytic hydrogenation reactions. Compared with other traditional catalysts, MOFs and derived porous carbon materials have some unique advantages as hydrogenation catalysts, which are described in this review. In addition, we have expounded the rational design of MOF hydrogenation catalysts from the following four aspects: choosing suitable MOFs with coordinated unsaturated metal sites, good stability, and precise control and optimizing the structure of MOF materials and hydrogen storage characteristics of MOF materials. The application of nitrogen-doped carbon materials and MOF-derived porous carbon materials in hydrogenation reactions has also been compared. Moreover, various MOFs and derived porous carbon materials with excellent performance are discussed in detail in various catalytic hydrogenation reactions including olefins, alkynes, alcohols and phenols, aldehydes, carboxylic acids, esters, nitro compounds, and other hydrogenation reactions. Finally, the challenges of MOFs and derived porous carbon materials as hydrogenation catalysts are objectively summarized, and the application and development trends in catalytic hydrogenation reactions are prospected.

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“…The direct hydroxylation of aromatic compounds to its corresponding phenols is a challenging task in synthetic organic chemistry. Phenols constitute an important class of biologically active compounds owing to their antibacterial, antihyperglycemic, antitumor, antiviral, antitumor, antimutagenicity, pro-oxidant, and cardioprotective properties. , Phenols and their derivatives are commonly used in industries and companies for the synthesis of fine chemicals, pharmaceuticals, and agrochemicals. , Phenolic motifs are also present in various natural products, such as terpenoids, macrolides, quinines, alkaloids, and aryl steroids. , Due to their prevalent importance, dedicated efforts have been put forward to ease the synthesis of phenols. To date, different approaches have been utilized for the synthesis of phenolic compounds like nucleophilic substitution of aryl halides by hydroxyl group, C–H aryl ring oxidation and hydrolysis of diazonium salts, hydroxylation of aryl halides using hydroxide salts, hydroxylation of aryl halides, and so on. − However, the use of toxic solvents, homogeneous catalysts, harsh reaction conditions, and expensive metal-based catalysts, tedious reaction workups, and longer reaction time made these processes undesirable for large scale applications. , …”

Section: Introductionmentioning

confidence: 99%

Surface Nanoarchitectonics of Boron Nitride Nanosheets for Highly Efficient and Sustainableipso-Hydroxylation of Arylboronic Acids

Choudhary

Kumari

Sharma

et al. 2023

ACS Appl. Mater. Interfaces

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One of the important industrial processes commonly employed in the pharmaceutical, explosive, and plastic manufacturing industries is ipso-hydroxylation of arylboronic acids. In this work, a straightforward, metal-free methodology for the synthesis of phenols from arylboronic acids has been demonstrated using hydroxyl functionalized boron nitride (BN−OH) nanosheets. The functionalized hydroxyl groups on the BN nanosheets act as the active sites for the hydroxylation reaction to take place. The detailed optimization of reaction parameters was done in order to attain high catalytic efficiency, and the reactions were conducted in water, which eliminates the use of toxic solvents. The as-synthesized catalysts exhibited excellent recyclability and reusability in addition to high product yields and good turnover numbers. The green metrics parameters were also evaluated for the model reaction to examine the sustainable nature of the developed protocol. The use of BN−OH catalysts for the ipso-hydroxylation reactions under base-free and metal-free conditions using environmentally benign solvents is utmost desired for industrial processes and can pave a way toward sustainable organic catalysis.

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Nickel-catalyzed oxidative hydroxylation of arylboronic acid: Ni(HBTC)BPY MOF as an efficient and ligand-free catalyst to access phenolic motifs

Cited by 17 publications

References 35 publications

Coordination Polymers as a Functional Material for the Selective Molecular Recognition of Nitroaromatics and ipso‐Hydroxylation of Arylboronic Acids

Coordination Polymers as a Functional Material for the Selective Molecular Recognition of Nitroaromatics and ipso‐Hydroxylation of Arylboronic Acids

Application of Metal–Organic Framework Materials and Derived Porous Carbon Materials in Catalytic Hydrogenation

Surface Nanoarchitectonics of Boron Nitride Nanosheets for Highly Efficient and Sustainableipso-Hydroxylation of Arylboronic Acids

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