- N, O-Bidentate ligand-tunable copper(II) complexes as a catalyst for Chan-Lam coupling reactions of arylboronic acids with 1 H-imidazole derivatives
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An efficient procedure for Chan-Lam coupling reactions of arylboronic acids with 1H-imidazole derivatives using N,O-bidentate ligand-tunable copper(ii) complexes as a catalyst under base-free conditions has been developed. This protocol features mild reac
- Jia, Xuefeng,Peng, Pai
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Read Online
- Deprotometalation-iodolysis and computed CH acidity of 1,2,3- and 1,2,4-triazoles. Application to the synthesis of resveratrol analogues
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1-Aryl- and 2-aryl-1,2,3-triazoles were synthesized by N-arylation of the corresponding azoles using aryl iodides. The deprotometalations of 1-phenyl-1,2,3-triazole and -1,2,4-triazole were performed using a 2,2,6,6-tetramethylpiperidino-based mixed lithi
- Nagaradja, Elisabeth,Bentabed-Ababsa, Ghenia,Scalabrini, Mathieu,Chevallier, Floris,Philippot, Stéphanie,Fontanay, Stéphane,Duval, Rapha?l E.,Halauko, Yury S.,Ivashkevich, Oleg A.,Matulis, Vadim E.,Roisnel, Thierry,Mongin, Florence
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- Cu(I)–N-heterocyclic carbene-catalyzed base free C–N bond formation of arylboronic acids with amines and azoles
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A new N-heterocyclic carbene (NHC) precursor of imidazolium chloride and its corresponding Cu(I)–NHC complex 1 was synthesized. The complex 1 was found to be a highly effective catalyst for Chan-Evans-Lam coupling of arylboronic acid with amines and azoles (including imidazole, pyrazole and triazole), without addition of base at room temperature. Various substituents on three substrates can be tolerated, giving the desired coupling products in good to excellent yields (62–94%). The method is practical and offers an alternative to the corresponding copper-catalyzed Chan-Evans-Lam process for the construction of C–N bonds.
- Zhang, Maoyuan,Xu, Zengbing,Shi, Dabin
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- A novel two-dimensional metal-organic framework as a recyclable heterogeneous catalyst for the dehydrogenative oxidation of alcohol and theN-arylation of azole compounds
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A novel metal-organic framework (MOF) with two-dimensional (2D) crystal structure was developed using Cu(NO3)2·3H2O and 2,2′,5,5′-tetramethoxy-[1,1′-biphenyl]-4,4′-dicarboxylic acid. Further, its structure was characterized using infrared spectroscopy, thermogravimetry, X-ray diffraction, and X-ray crystallography. The activated Cu-MOF was used to catalyze the dehydrogenative oxidation of alcohol andN-arylation of azole compounds. Furthermore, it could be easily recovered and reused.
- Liu, Chengxin,Cui, Jin,Wang, Yufang,Zhang, Mingjie
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p. 11739 - 11744
(2021/03/31)
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- A ligand-free copper-catalyzed strategy to the N-arylation of indazole using aryl bromides
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A simple and efficient strategy for the C–N cross-coupling of indazole with a variety of substituted aryl bromides is reported. Under the optimized conditions, a broad scope of N-arylated products were obtained in good to excellent yields (up to 87%) under the ligand-free conditions.
- Bai, Di-Xiang,Lim, Rachel Sin-Ee,Ng, Hui-Fen,Teo, Yong-Chua
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supporting information
p. 1398 - 1405
(2021/03/08)
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- Facile One-Pot Synthesis of Methyl 1-Aryl-1H-1,2,4-triazole-3-carboxylates from Nitrilimines with Vilsmeier Reagent
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Two convenient and effective one-pot methods have been developed to synthesize methyl 1-aryl-1H-1,2,4-triazole1–3-carboxylates by using hydrazonoyl hydrochlorides (nitrilimines) with Vilsmeier reagent. The first, a direct one-pot method, involved the reac
- Tsai, Shuo-En,Chiang, Kun-Heng,Tseng, Ching-Chun,Chen, Nai-Wei,Chern, Ching-Yuh,Wong, Fung Fuh
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p. 1754 - 1762
(2019/02/24)
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- Preparation method of diarylamine compound
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The invention relates to a preparation method of a diarylamine compound. Specifically, under the catalysis of cuprous oxide supported by chitosan, the arylation reaction used for a nitrogen-containingheterocyclic compound is achieved, and the corresponding diarylamine compound is obtained. The preparation method of the diarylamine compound has the advantages that the process conditions are simple, the yield is good, the operability is strong, and the functional group tolerance is wide.
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Paragraph 0070; 0071; 0072
(2019/04/26)
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- Recyclable bimetallic CuMoO4 nanoparticles for C-N cross-coupling reaction under mild conditions
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Herein we disclosed inexpensive copper(ii) bimetallic CuMoO4 nanoparticles for the C-N cross-coupling reaction of alkyl and aryl amines with haloarenes. The reaction proceeds under mild and ligand free conditions. The catalyst is recyclable and effective for a wide range of amines and haloarenes. Here, the efficiency of the Cu(ii) catalyst is increased by doping molybdenum metal. The bimetallic nanoparticles are anticipated to proceed via normal oxidative addition and reductive eliminations.
- Panigrahi, Reba,Panda, Subhalaxmi,Behera, Pradyota Kumar,Sahu, Santosh Kumar,Rout, Laxmidhar
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supporting information
p. 19274 - 19278
(2019/12/24)
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- Synergistic catalysis for light-driven proton reduction using a polyoxometalate-based Cu-Ni heterometallic-organic framework
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Synergistic effects of bimetallic Ni and Cu supported on metal-organic polymer composites based on Wells-Dawson P2W18O626- clusters as photosensitizer units were identified, and we report a novel approach for addressing these issues for dehydrogenation and hydrogen production reactions.
- Sun, Wenlong,He, Cheng,Liu, Tao,Duan, Chunying
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supporting information
p. 3805 - 3808
(2019/04/01)
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- C?N Cross-Coupling Reactions Under Mild Conditions Using Singlet Di-Radical Nickel(II)-Complexes as Catalyst: N-Arylation and Quinazoline Synthesis
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Herein we report a cost-effective synthetic approach for C?N cross-coupling reactions of a broad array of nitrogen nucleophiles and aryl halides under mild conditions. These reactions are catalyzed by an inexpensive, air-stable, earth-abundant and easy-to-prepare singlet di-radical nickel(II)-catalyst containing two antiferromagnetically coupled single-electron oxidized diiminosemiquinonato type ligands. This protocol provides an alternative method for C?N cross-coupling reactions avoiding nickel(0)/nickel(II) or nickel(I)/nickel(III) redox processes via cooperative participation of metal and ligand-centered redox events. Besides a wide range of N-arylation reactions, by judicious choice of aryl halides and nitrogen nucleophiles the synthesis of a variety of polysubstituted quinazolines has been achieved in moderate to good yields under relatively mild reaction conditions. Our catalyst has been found to be almost equally effective in quinazoline synthesis via C?N cross-coupling of (i) 2-bromobenzylamine with benzamide, and (ii) 2-bromobenzylbromide with amidine. Control experiments and DFT studies were performed to improve the understanding of the cooperative participation of ligand and metal (nickel)-centered redox events during oxidative addition/reductive elimination processes of the catalytic cycle and to shed light on the plausible mechanistic pathway of the C?N cross-coupling reactions. (Figure presented.).
- Sikari, Rina,Sinha, Suman,Chakraborty, Gargi,Das, Siuli,van Leest, Nicolaas Petrus,Paul, Nanda D.
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supporting information
p. 4342 - 4353
(2019/08/21)
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- Iron-Catalyzed/Mediated C-N Bond Formation: Competition between Substrate Amination and Ligand Amination
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Iron catalyzed carbon-nitrogen bond formation reactions of a wide variety of nucleophiles and aryl halides using well-defined iron-complexes featuring redox noninnocent 2-(arylazo)-1,10-phenanthroline (L1) ligands are reported. Besides substrate centered C-N coupling, C-N bond formation reactions were also observed at the ortho- and para-positions of the phenyl ring of the coordinated azo-aromatic scaffolds affording new tetradentate ligands, 2-N-aryl-(2-arylazo)-1,10-phenanthroline (L2), and tridentate ligands, 4-N-aryl-(2-arylazo)-1,10-phenanthroline (L3), respectively. Control experiments and mechanistic studies reveal that the complex [FeL1Cl2] (1) undergoes in situ reduction during the catalytic reaction to produce the monoanionic complex [1]-, which then acts as the active catalyst. The metal (iron) and the coordinated ligand were found to work in a cooperative manner during the transfer processes involved in the fundamental steps of the catalytic cycle. Detailed experimental and theoretical (DFT) studies were performed to get insight into the competitive substrate versus ligand centered amination reactions.
- Sinha, Suman,Sikari, Rina,Sinha, Vivek,Jash, Upasona,Das, Siuli,Brand?o, Paula,Demeshko, Serhiy,Meyer, Franc,De Bruin, Bas,Paul, Nanda D.
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p. 1935 - 1948
(2019/01/25)
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- A Multicomponent Electrosynthesis of 1,5-Disubstituted and 1-Aryl 1,2,4-Triazoles
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A novel electrochemical route has been developed for the synthesis of 1,5-disubstituted and 1-aryl 1,2,4-triazoles from aryl hydrazines, paraformaldehyde, NH4OAc, and alcohols. In this multicomponent reaction system, alcohols act as solvents as well as reactants and NH4OAc is used as the nitrogen source. With the assistance of reactive iodide radical or I2 and NH3 electrogenerated in situ, this process could effectively avoid the use of strong oxidants and transition-metal catalysts and be smoothly carried out at room temperature to give a wide array of 1,2,4-triazole derivatives in good to high yields. Preliminary studies reveal that the reaction mechanism involves a radical process.
- Yang, Na,Yuan, Gaoqing
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p. 11963 - 11969
(2018/09/25)
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- Novel tertiary sulfonamides as potent anti-cancer agents
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For adult women in the United States, breast cancer is the most prevalent form of cancer. Compounds that target dysregulated signal transduction can be efficacious anti-cancer therapies. A prominent signaling pathway frequently dysregulated in breast canc
- Okolotowicz, Karl J.,Dwyer, Mary,Ryan, Daniel,Cheng, Jiongjia,Cashman, Emily A.,Moore, Stephanie,Mercola, Mark,Cashman, John R.
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p. 4441 - 4451
(2018/08/03)
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- Hydrophobic spontaneous combustion N-hydrocarbonyl triazole dicyanoborane complex and preparation method thereof
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The invention relates to a hydrophobic spontaneous combustion N-hydrocarbonyl triazole dicyanoborane complex and a preparation method thereof. The structure of the N-hydrocarbonyl triazole dicyanoborane complex is shown as a formula I. The method for prep
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Paragraph 0057; 0060
(2018/09/21)
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- Efficient and recyclable copper-based MOF-catalyzed N-arylation of N-containing heterocycles with aryliodides
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Copper-based MOF-199 was used as an efficient heterogeneous catalyst to catalyze cross-coupling reactions between N-containing heterocycles and aryliodides with high yields. The catalyst can be easily separated from the reaction mixture, and can be reused at least 5 times without significantly decreasing the activity. The XRD results showed that the crystallinity and structure of MOF-199 can be maintained well during the coupling reaction.
- Li, Zihao,Meng, Fei,Zhang, Jie,Xie, Jianwei,Dai, Bin
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supporting information
p. 10861 - 10865
(2016/12/06)
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- Synthesis of 1-substituted 3-amino-1H-1,2,4-triazoles from ethyl N-(5-phenyl-1,2,4-oxadiazol-3-yl)formimidate
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Abstract A general and efficient method for the synthesis of 1-substituted 3-amino-1H-1,2,4-triazoles has been developed. The desired 3-amino-1H-1,2,4-triazoles (3) were prepared in good to excellent yields from ethyl N-(5-phenyl-1,2,4-oxadiazol-3-yl)form
- Shen, Jeff,Zhang, Haiming
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p. 6164 - 6169
(2015/08/03)
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- Tamarix gallica leaf extract mediated novel route for green synthesis of CuO nanoparticles and their application for N-arylation of nitrogen-containing heterocycles under ligand-free conditions
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We report the green synthesis of CuO nanoparticles (CuO NPs) using Tamarix gallica leaf extract and their catalytic activity for N-arylation of nitrogen-containing heterocycles with aryl halides under ligand-free conditions. Tamarix gallica leaves are used as a bio-material for the first time as reducing agent. The green synthesized CuO NPs was characterized using the powder XRD, TEM, UV-vis and FT-IR. This method offers several advantages, viz. high yields, simple methodology, recyclability of the catalyst and a simple workup procedure.
- Nasrollahzadeh, Mahmoud,Sajadi, S. Mohammad,Maham, Mehdi
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p. 40628 - 40635
(2015/05/20)
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- Blue phosphorescent N-heterocyclic carbene chelated Pt(ii) complexes with an α-duryl-β-diketonato ancillary ligand
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C^C chelated Pt(ii) compounds that contain an N-heterocyclic carbene (NHC) donor have recently attracted great interest as blue or white phosphorescent emitters for organic light-emitting devices (OLEDs). To overcome the tendency for excimer formation in Pt(ii) compounds, an α-duryl-β-diketonato ligand was selected as the ancillary ligand for blue phosphorescent C^C chelated Pt(ii) compounds. Using this approach, a series of NHC-based C^C chelated Pt(ii) compounds has been designed and synthesized. The chelate ligands used in the new C^C chelated Pt(ii) compounds include 1-phenylimidazol-2-ylidene in Pt1, 1-phenyl-1,2,4-triazol-5-ylidene in Pt2, p-TMS-1-phenylimidazol-2-ylidene in Pt3, and p-TMS-1-phenyl-1,2,4-triazol-5-ylidene in Pt4. A single-crystal X-ray diffraction analysis revealed that the presence of the α-duryl-β-diketonato ligand in the Pt(ii) compounds effectively suppresses the dimer formation in the crystal lattice. Pt1, Pt2, Pt3, and Pt4 display blue phosphorescence at room temperature. The p-TMS substituted complex Pt3 was found to display the most efficient blue phosphorescence at λem = 468 nm with a ΦPL of 0.68. Spectroscopic and computational studies established that the blue phosphorescence in the phenyl-imidazolylidene chelated complexes originates mainly from a 3MLCT state while that in the phenyl-triazolylidene chelated compounds arises from a 3ILCT state. Electroluminescent devices using Pt1 and Pt3 as the dopant were fabricated which display both monomer and exciplex emission, leading to pure white light electroluminescence with CIE coordinates of (0.32, 0.31).
- Ko, Soo-Byung,Park, Hee-Jun,Gong, Shaolong,Wang, Xiang,Lu, Zheng-Hong,Wang, Suning
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p. 8433 - 8443
(2015/05/20)
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- Microwave-assisted catalyst-free synthesis of substituted 1,2,4-triazoles
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A simple, efficient, and mild method has been developed for the synthesis of substituted 1,2,4-triazoles from hydrazines and formamide under microwave irradiation. The reaction proceeds smoothly in the absence of a catalyst and shows excellent functional-group tolerance.
- Shelke, Ganesh M.,Rao, V. Kameswara,Jha, Mukund,Cameron, T. Stan,Kumar, Anil
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p. 404 - 407
(2015/02/19)
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- Copper-catalyzed arylation of nitrogen heterocycles from anilines under ligand-free conditions
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The arylation of pyrazole and derivatives can be achieved by coupling arenediazonium species (formed in situ from anilines) by using a catalytic system that employs low-toxicity and inexpensive copper metal under very mild and ligand-free conditions (T = 20 ° C). From other nitrogen heterocycles, the presence of an additive (NBu4I) significantly improves the efficiency of the catalytic system. These results represent the first examples of C-N bond formation from arenediazonium species.
- Toummini, Dounia,Tlili, Anis,Bergs, Julien,Ouazzani, Fouad,Taillefer, Marc
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supporting information
p. 14619 - 14623
(2015/01/09)
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- Copper(I) 3-methylsalicylate, an efficient catalyst for N-arylation of heterocycles under moderate reaction conditions
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Copper(I) 3-methylsalicylate mediates N-arylation reactions of both aliphatic and aromatic heterocycles under moderate reaction conditions. Both electron rich and electron poor aryl bromides and a diverse set of N-heterocycles were allowed to react and gave N-arylation products in high yields which demonstrated the efficiency and utility of this catalyst.
- Farahat, Abdelbasset A.,Boykin, David W.
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supporting information
p. 3049 - 3051
(2014/05/20)
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- Aromatic N-arylations catalyzed by copper-anchored porous zinc-based metal-organic framework under heterogeneous conditions
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A highly porous Zn-based metal-organic framework (MOF) IRMOF-3 was covalently decorated with pyridine-2-aldehyde. The free amine group of IRMOF-3 upon condensation with pyridine-2-aldehyde affords a bidentate Schiff-base moiety in the porous matrix. The Schiff base moieties are availed to anchor copper(II) ions to display the catalyst's utility towards catalytic reactions. The catalyst was characterized by UV/Vis and IR spectroscopy, powder XRD spectrometry, SEM energy-dispersive X-ray spectrometry, and nitrogen sorption measurements. The catalyst exhibits excellent activity in catalyzing the N-arylation reaction of nitrogen-containing heterocycles with aryl bromides in DMSO medium, under mild condition (90°C) in the presence of Cs 2CO3. The porous catalyst demonstrates size selectivity towards substrate as a result of the presence of active sites inside the pores of the MOF. The anchored complex seems to be not leached or decomposed during the catalytic reactions up to five successive catalytic cycles, demonstrating practical advantages over homogeneous catalysis.
- Maity, Tanmoy,Saha, Debraj,Koner, Subratanath
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p. 2373 - 2383
(2014/08/18)
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- Highly active recyclable heterogeneous Pd/ZnO nanoparticle catalyst: Sustainable developments for the C-O and C-N bond cross-coupling reactions of aryl halides under ligand-free conditions
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Efficient Pd supported on ZnO nanoparticles for the ligand-free O-arylation and N-arylation of phenols and various N-H heterocycles with aryl chlorides, bromides, and iodides were readily synthesized and characterized. The amount of palladium on ZnO is 9.84 wt% (0.005 g of the catalyst contains 462 × 10-8 mol% of Pd) which was determined by ICP analysis. This nano sized Pd/ZnO with an average particle size of 20-25 nm and specific surface area 40.61 m2 g-1 was used as a new reusable heterogeneous catalyst for the formation of C-O and C-N bonds in organic synthesis. This protocol gives the arylated product in satisfactory yields without any N2 or Ar flow. The catalyst can be recovered and recycled several times without marked loss of activity.
- Hosseini-Sarvari, Mona,Razmi, Zahra
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p. 44105 - 44116
(2014/12/10)
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- Nano copper(i) oxide/zinc oxide catalyzed N-arylation of nitrogen-containing heterocycles with aryl halides and arylboronic acids in air
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The synergistic effect of zinc and copper in Cu2O/ZnO nanoflake as a heterogeneous catalyst for the N-arylation of heterocycles with aryl halides and arylboronic acids in the absence of additional ligand in air were demonstrated. The catalyst was characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), BET surface area measurement, and FT-IR spectroscopy. The Royal Society of Chemistry 2014.
- Hosseini-Sarvari, Mona,Moeini, Fatemeh
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p. 7321 - 7329
(2014/02/14)
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- Triazole-substituted nitroarene derivatives: Synthesis, characterization, and energetic studies
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A series of dense and energetic polynitroaryl-1,2,4-triazoles were synthesized through the nitration of aryl-1,2,4-triazoles. The Cu-catalyzed/base-mediated coupling reactions of haloarenes with 1,2,4-triazoles delivered N-aryl-1,2,4-triazoles. These new
- Kommu, Nagarjuna,Ghule, Vikas D.,Kumar, A. Sudheer,Sahoo, Akhila K.
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supporting information
p. 166 - 178
(2014/01/06)
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- Synthesis and crystal structures of coordination complexes containing Cu2I2 units and their application in luminescence and catalysis
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The reaction of bis- or tris-chelating nitrogen-containing ligands (L1-L5) with CuI gave rise to five coordination complexes consisting of Cu 2I2 dimeric units. L1 in complex 1 adopts a cis conformation and links Cu2I2 into a dinuclear structure. L2 and L3 in complexes 2 and 3 exhibit a trans conformation, and the alternative linkage of L2 or L3 and Cu2I2 results in the formation of a 1D chain. In complex 4, two pyrazolyl-pyridine units of L4 at the same side of the central phenyl ring are connected to Cu2I2 forming a tetranuclear macrocycle, and the third pyrazolyl-pyridine unit at the other side of the central phenyl ring further links the macrocycle into a 1D chain. L5 bridges Cu2I2 in a cis conformation forming a tetranuclear complex, which is very different from 1 owing to the difference of the electronic property between pyrazolyl and triazolyl rings. The coordination nitrogen atoms in two pairs of ortho-positioned nitrogen-containing chelating rings in L1 and L5 are directed toward opposite and the same directions, respectively. Complexes 1-4 containing pyrazolyl-pyridine units showed luminescence whereas no clear emission was observed in complex 5 containing triazolyl-pyridine units, despite the fact that they were investigated under the same conditions. The application of complexes 1-5 in the copper(I)-catalyzed Ullmann cross-coupling reaction and azide-alkyne cycloaddition reaction was preliminarily evaluated. Making a difference: Five copper(I) complexes consisting of Cu2I2 units (see figure for example) have been prepared by using readily available bis- or tris-chelating nitrogen-containing ligands. These complexes possess different crystal structures, luminescence properties, and catalytic performances owing to the difference in steric and electronic properties of the organic ligands. Copyright
- Zhao, Huaixia,Li, Xinxiong,Wang, Jinyun,Li, Liuyi,Wang, Ruihu
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p. 1491 - 1502
(2014/01/06)
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- The fluorine-NHC gauche effect: A structural and computational study
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Herein, we report the synthesis and X-ray structural analysis of a collection of fluorinated metal N-heterocyclic carbenes (Ag, Au, Pd, Rh, Ir) and their precursor salts. The common structural feature of these species is a flanking fluoroethyl group, which is either freely rotating or embedded within a bicyclic framework. Solid state analysis confirmed a gauche conformational preference in all cases with the fluorine adopting a syn clinal arrangement (φ[NCCF]~60°) with respect to the triazolium nitrogen at the vicinal position of the NHC. A density functional theory analysis was employed to quantify these effects and evaluate the influence of electronic modulation of the carbenic carbon [(CN+); neutral carbene (C:); metal-bound carbene (CM)], on the relative gauche/anti preference, thus highlighting the potential of this conformational phenomenon as a useful molecular design strategy for controlling the topology of organometallic complexes.
- Paul, Susann,Schweizer, W. Bernd,Rugg, Graham,Senn, Hans Martin,Gilmour, Ryan
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supporting information
p. 5647 - 5659
(2013/07/11)
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- Ligand-free CuSO4-catalyzed C-N coupling reaction of aryl halides with alkylamines or N-heterocycles in aqueous solution system
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C-N coupling can be achieved successfully under 80°C in aqueous nBu4NOH using CuSO4 as a catalyst. The study of substrate applicability demonstrated that the C-N coupling reaction of aryl iodides and bromides with alkylamines or N-heterocycles could be completed smoothly in this catalytic system.
- Yang, Hua,Zhang, Xiuli,Si, Jingyu
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p. 5647 - 5648
(2013/07/26)
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- A highly efficient Cu-catalyst system for N-arylation of azoles in water
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6,7-Dihydroquinolin-8(5H)-one oxime (L3) was found to serve as a superior ligand for the CuI-catalyzed N-arylation of imidazoles with aryl iodides, bromides, and electron-deficient chlorides in water. Moreover, the CuI/L3 catalyst system enabled the coupling reactions to take place smoothly with high yields under a low catalyst loading (0.1-1 mol% CuI and 0.2-2 mol% L3).
- Wang, Deping,Zhang, Fuxing,Kuang, Daizhi,Yu, Jiangxi,Li, Junhua
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supporting information; experimental part
p. 1268 - 1271
(2012/06/04)
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- 1,2,4-triazole-based tunable aryl/alkyl ionic liquids
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Ionic liquids based on aryl-/alkyl-substituted imidazolium salts constitute a new generation of ionic liquids with a high degree of flexibility. The new concept could now also be extended to aryl-/alkyl-substituted 1,2,4-triazolium salts. The two differen
- Meyer, Dirk,Strassner, Thomas
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supporting information; experimental part
p. 305 - 308
(2011/03/20)
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- Salts Comprising Aryl-Alkyl-Substituted Imidazolium and Triazolium Cations and the Use Thereof
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The present invention relates to salts comprising novel aryl-alkyl-substituted imidazolium and triazolium cations and arbitrary anions. The invention further relates to methods for the chemical conversion and separation of substances, comprising the salts
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Page/Page column 38-39
(2011/05/08)
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- Impact of ligand modification on structures and catalytic activities of chelating bis-carbene rhodium(I) complexes
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A series of novel chelating N-heterocyclic bis-carbene rhodium(I) complexes based on 1,2,4-triazoles, benzimidazoles, and imidazoles with varying bridge length and N substituents has been synthesized. In addition to their structural characterization, thei
- Riederer, Stephanie K. U.,Gigler, Peter,Hoegerl, Manuel P.,Herdtweck, Eberhardt,Bechlars, Bettina,Herrmann, Wolfgang A.,Kuehn, Fritz E.
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experimental part
p. 5681 - 5692
(2011/01/12)
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- Synthesis and antitumor activity of 1,5-disubstituted 1,2,4-triazoles as cis-restricted combretastatin analogues
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A series of 1-aryl-5-(3′,4′,5′-trimethoxyphenyl) derivatives and their related 1-(3′,4′,5′-trimethoxyphenyl)-5- aryl-1,2,4-triazoles, designed as cis-restricted combretastatin analogues, were synthesized and evaluated for antiproliferative activity, inhibitory effects on tubulin polymerization, cell cycle effects, and apoptosis induction. Their activity was greater than, or comparable with, that of the reference compound CA-4. Flow cytometry studies showed that HeLa and Jurkat cells treated with the most active compounds 4l and 4o were arrested in the G2/M phase of the cell cycle in a concentration dependent manner. This effect was accompanied by apoptosis of the cells, mitochondrial depolarization, generation of reactive oxygen species, activation of caspase-3, and PARP cleavage. Compound 4l was also shown to have potential antivascular activity, since it induced endothelial cell shape change in vitro and disrupted the sprouting of endothelial cells in the chick aortic ring assay.
- Romagnoli, Romeo,Baraldi, Pier Giovanni,Cruz-Lopez, Olga,Lopez Cara, Carlota,Carrion, Maria Dora,Brancale, Andrea,Hamel, Ernest,Chen, Longchuan,Bortolozzi, Roberta,Basso, Giuseppe,Viola, Giampietro
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supporting information; experimental part
p. 4248 - 4258
(2010/09/05)
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- Mild conditions for copper-catalyzed N-arylation of imidazoles
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An efficient copper(I) bromide catalyzed N-arylation of azoles with a variety of aromatic bromides and iodides under mild conditions is reported. This reaction displayed great functional group compatibility and excellent reactive selectivity. Georg Thieme Verlag Stuttgart.
- Chen, Huaming,Wang, Deping,Wang, Xianyang,Huang, Wenlong,Cai, Qian,Ding, Ke
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experimental part
p. 1505 - 1511
(2010/09/14)
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- Per-6-amino-β-cyclodextrin as an efficient supramolecular ligand and host for Cu(I)-catalyzed N-arylation of imidazole with aryl bromides
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(Chemical Presented) Per-6-amino-β-cyclodextrin (per-6-ABCD), acting simultaneously as a supramolecular ligand for CuI and host for aryl bromides, catalyzes N-arylation of imidazole with aryl bromides under mild conditions. This simple method proceeds with excellent yield for the coupling of imidazole with various substituted aryl bromides demonstrating good tolerance of other functionalities.
- Suresh, Palaniswamy,Pitchumani, Kasi
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experimental part
p. 9121 - 9124
(2009/04/11)
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- N-arylations of nitrogen-containing heterocycles with aryl and heteroaryl halides using a copper(I) oxide nanoparticle/1,10-phenanthroline catalytic system
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A general procedure for solvent-free N-arylations of nitrogen-containing heterocycles, i.e. imidazoles, triazoles, and indoles, with aryl and heteroaryl halides catalyzed by copper(I) oxide (Cu2O) nanoparticles is demonstrated. Four types of Cu2O were evaluated: the bulky compound and its cubic, octahedral, and spherical nanoparticulate forms. The results show that Cu2O nanoparticles, in particular the cubic form, are highly efficient for the N-arylation reaction. In the presence of cubic Cu2O nanoparticles, 1,10-phenanthroline, and tetrabutylammonium fluoride, a variety of nitrogen-containing heterocycles smoothly underwent N-arylation with aryl and heteroaryl halides at 110-145 °C to give the corresponding products in moderate to excellent yields. It is noteworthy that the reaction is conducted under solvent-free conditions. The reaction mechanism is also discussed.
- Tang, Bo-Xiao,Guo, Sheng-Mei,Zhang, Man-Bo,Li, Jin-Heng
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p. 1707 - 1716
(2008/12/22)
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- Copper-catalyzed N-arylation of amides and azoles using phosphine-free hydrazone ligands
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Phosphine-free hydrazone such as 1c was found to be an efficient ligand for the copper-catalyzed Goldberg-type N-arylation of amides and Ullmann-type N-arylation of azoles with aryl halides under mild conditions. A variety of N-arylamides and N-arylazoles were synthesized in good to high yields. Georg Thieme Verlag Stuttgart.
- Mino, Takashi,Harada, Yoshikazu,Shindo, Hiroaki,Sakamoto, Masami,Fujita, Tsutomu
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p. 614 - 620
(2008/12/22)
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- IRON-COPPER CO-CATALYZED PROCESS FOR CARBON-CARBON OR CARBON-HETEROATOM BONDING
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The present invention relates to a process for creating a Carbon-Carbon bond (C-C) or a Carbon-Heteroatom bond (C -HE) by reacting a compound carrying a leaving group with a nucleophilic compound carrying a carbon atom or a heteroatom (HE) that can substitute for the leaving group, creating a C-C or C-HE bond, wherein the reaction takes place in the presence of an effective quantity of a catalytic system comprising iron and copper.
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Page/Page column 48-49
(2008/06/13)
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- Highly practical "ligand-free-like" copper-catalyzed N-arylation of azoles in lower nitrile solvents
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In lower nitrile solvents, the N-arylation of azoles with aryl halides was achieved efficiently in the presence of copper powder without any additional ligands. Thus, the first nitrile type of monodentate ligand-mediated, "ligand-free-like" copper-catalyzed N-arylation procedure was established.
- Zhu, Rui,Xing, Lixin,Wang, Xinyan,Cheng, Chuanjie,Su, Deyong,Hu, Yuefei
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supporting information; experimental part
p. 1253 - 1257
(2009/06/18)
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- Solvent-free copper/iron co-catalyzed N-arylation reactions of nitrogen-containing heterocycles with trimethoxysilanes in air
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A solvent-free copper/iron-catalyzed N-arylation of nitrogen-containing heterocycles with trimethoxysilanes method for the formation of C-N bonds has been developed. In the presence of Cu, FeCl3, TBAF, and air, a variety of nitrogen-containing heterocycles including imidazoles and triazoles were coupled with aryltrimethoxysilanes and vinyltrimethoxysilane to afford the corresponding products in moderate to excellent yields. It is noteworthy that the reaction is conducted under solvent-free and relatively low Cu/FeCl3 loadings conditions.
- Song, Ren-Jie,Deng, Chen-Liang,Xie, Ye-Xiang,Li, Jin-Heng
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p. 7845 - 7848
(2008/03/11)
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- Simple copper salt-catalyzed N-arylation of nitrogen-containing heterocycles with aryl and heteroaryl halides
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(Chemical Equation Presented) Relatively mild and highly efficient CuI-catalyzed N-arylation procedures for nitrogen-containing heterocycles (e.g., imidazoles, benzimidazoles, pyrroles, pyrazoles, indoles, triazoles, etc.) with aryl and heteroaryl halides have been developed. The protocols can be performed easily and tolerate a number of functional groups, such as ester, nitrile, nitro, ketone, free hydroxyl, and free primary amine on the aryl halide.
- Zhu, Liangbo,Guo, Peng,Li, Gaocan,Lan, Jingbo,Xie, Rugang,You, Jingsong
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p. 8535 - 8538
(2008/03/11)
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- Efficient iron/copper co-catalyzed arylation of nitrogen nucleophiles
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(Chemical Equation Presented) An ideal pair: Various substituted aryl halides react under mild conditions with nitrogen heterocycles in the presence of catalytic amounts of [Fe(acac)3] (acac = acetylacetonate) and copper salts to give the corresponding cross-coupling products in high yields (see scheme). This cheap and environmentally friendly cocatalyst system is the first example of cooperative Fe/Cu catalysis in this type of N-C bond formation.
- Taillefer, Marc,Xia, Ning,Ouali, Armelle
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p. 934 - 936
(2008/02/01)
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- A concept of supported amino acid ionic liquids and their application in metal scavenging and heterogeneous catalysis
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Novel supported task-specific ionic liquids have been developed for the first time via the ionic-pair coupling of imidazolium cation of the modified polystyrene support with L-proline. The materials have shown an efficient metal scavenging ability (e.g., Cul, Pd(OAc)2, Pd0, and IrCl3) without the aid of a nonimmobilized ionic liquid, which relies on the highly synergistic effect of the coordination with the nitrogen atom and the COO- group of the L-proline moiety, electrostatic forces, and steric protection. The resulting metal-soaked supported ionic liquids can be used as efficient heterogeneous catalysts. These materials have been investigated in the Cul-catalyzed N-arylation of nitrogen-containing heterocycles and exhibit much higher catalytic activity and a more extensive structural range of aryl and heteroaryl halides than those exhibited by free L-proline in combination with Cul both in the ionic liquid ([BMIM][BF 4]) and in the corresponding homogeneous reaction conditions. The Cul-soaked catalyst 4a-2 can be recycled for nine runs at least without any considerable loss of activity. To the best of our knowledge, our catalytic process is among the most efficient approaches to the N-arylation of imidazoles with aryl halides so far reported. Furthermore, the Pd-soaked material 4a-2 also shows higher catalytic activity in the solvent-free hydrogenation of styrene to ethylbenzene. This new concept is generally applicable and may easily be extended to other supported task-specific ionic liquids.
- Chen, Wen,Zhang, Yuanyuan,Zhu, Liangbo,Lan, Jingbo,Xie, Rugang,You, Jingsong
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p. 13879 - 13886
(2008/09/16)
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- Highly efficient copper-catalyzed N-arylation of nitrogen-containing heterocycles with aryl and heteroaryl halides
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(Chemical Equation Presented) New (S)-pyrrolidinylmethylimidazole ligands (4a-c) have been readily synthesized in a straightforward fashion from least expensive starting materials in short steps in high yields. Relatively mild and highly efficient Cul-catalyzed N-arylation procedures for imidazoles with aryl and heteroaryl bromides or chlorides have been developed in the presence of 4a and Cs2CO3. It is important to note that the protocol could tolerate functional groups such as ester, nitrile, nitro, ketone, free hydroxyl, and free primary amine on the aryl halide. The protocol could also be applicable to other π-electron-rich nitrogen heterocycles (pyrrole, pyrazole, indole, benzimidazole, and triazole), affording the N-arylazoles in good to excellent yields.
- Zhu, Liangbo,Cheng, Liang,Zhang, Yuxi,Xie, Rugang,You, Jingsong
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p. 2737 - 2743
(2008/02/05)
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- Ligand-free copper-catalyzed N-arylation of nitrogen nucleophiles
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Versatile, simple and inexpensive ligand-free, copper-catalyzed N-arylations of sulfoximines and nitrogen-containing heterocycles have been developed affording N-arylated products in high yields.
- Correa, Arkaitz,Bolm, Carsten
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p. 2673 - 2676
(2008/09/19)
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- N-Arylation of aliphatic, aromatic and heteroaromatic amines catalyzed by copper bis(2,2,6,6-tetramethyl-3,5-heptanedionate)
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Copper bis(2,2,6,6-tetramethyl-3,5-heptanedionate) was found to be an efficient catalyst for N-arylation of aliphatic, aromatic and heteroaromatic amines with aryl iodides/bromides under mild conditions. The system tolerated a variety of hindered and functionalized amines/aryl halides and the desired N-aryl amines were obtained in good to excellent yields.
- Nandurkar, Nitin S.,Bhanushali, Mayur J.,Bhor, Malhari D.,Bhanage, Bhalchandra M.
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p. 6573 - 6576
(2008/02/12)
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- Method of forming a carbon-carbon or carbon-heteroatom linkage
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The invention relates to a method of creating a carbon-carbon or carbon-heteroatom linkage by reacting an unsaturated compound bearing a leaving group and a nucleophilic compound. More specifically, the invention relates to the creation of a carbon-nitrogen linkage involving the arylation of nitrogenous organic derivatives. The inventive method consists in creating a carbon-carbon or carbon-heteroatom linkage by reacting an unsaturated compound bearing a leaving group and a nucleophilic compound providing a carbon atom or a heteroatom (HE) capable of being substituted for the leaving group, thereby creating a C—C or C-HE linkage. The invention is characterised in that the reaction is carried out in the presence of an effective quantity of a catalyst based on copper and at least one ligand comprising at least one imine function and at least one additional nitrogen atom as chelating atoms
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Page/Page column 23; 28-29
(2010/02/14)
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- Copper-diamine-catalyzed N-arylation of pyrroles, pyrazoles, indazoles, imidazoles, and triazoles
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This paper details the copper-catalyzed N-arylation of π-excessive nitrogen heterocycles. The coupling of either aryl iodides or aryl bromides with common nitrogen heterocycles (pyrroles, pyrazoles, indazoles, imidazoles, and triazoles) was successfully performed in good yield with catalysts derived from diamine ligands and CuI. General conditions were found that tolerate functional groups such as aldehydes, ketones, alcohols, primary amines, and nitriles on the aryl halide or heterocycle. Hindered aryl halides or heterocycles were also found to be suitable substrates using the conditions reported herein.
- Antilla, Jon C.,Baskin, Jeremy M.,Barder, Timothy E.,Buchwald, Stephen L.
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p. 5578 - 5587
(2007/10/03)
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- Highly efficient and mild copper-catalyzed N- and C-arylations with aryl bromides and iodides
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Mild, efficient, copper-catalyzed N-arylation procedures for nitrogen heterocycles, amides, carbamates, and C-arylation procedures for malonic acid derivatives have been developed that afford high yields of arylated products with excellent selectivity. The N-arylation of imidazole with aryl bromides or iodides was found to be greatly accelerated by inexpensive, air-stable catalyst systems, combining catalytic copper salts or oxides with a set of structurally simple chelating ligands. The reaction was shown to be compatible with a broad range of aryl halides, encompassing sterically hindered, electron-poor, and electron-rich ones, providing the arylated products under particularly mild conditions (50-82°C). The lower limit in ligand and catalyst loading and the scope of Ullmann-type condensations catalyzed by complexes bearing those ligands with respect to the nucleophile class have also been investigated. Chelating Schiff base Chxn-Py-Al (1c) generates a remarkably general copper catalyst for N-arylation of pyrrole, indole, 1,2,4-triazole, amides, and carbamates; and C-arylation of diethyl malonate, ethyl cyanoacetate, and malononitrile with aryl iodides under mild conditions (50-82°C). The new method reported here is the most successful to date with regard to Ullmann-type arylation of some of these nucleophiles.
- Cristau, Henri-Jean,Cellier, Pascal P.,Spindler, Jean-Francis,Taillefer, Marc
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p. 5607 - 5622
(2007/10/03)
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- Process for arylating or vinylating or alkynating a nucleophilic compound
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The present invention concerns a process for arylating or vinylating or alkynating a nucleophilic compound. More particularly, the invention concerns arylating nitrogen-containing organic derivatives. The arylating or vinylating or alkynating process of the invention consists of reacting a nucleophilic compound with a compound carrying a leaving group and is characterized in that the reaction is carried out in the presence of an effective quantity of a catalyst based on a metallic element M selected from groups (VIII), (Ib) and (IIb) of the periodic table and at least one ligand comprising at least one imine function and at least one supplemental nitrogen atom as the chelating atoms.
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