10040-95-6Relevant articles and documents
Amino acid promoted CuI-catalyzed C-N bond formation between aryl halides and amines or N-containing heterocycles
Zhang, Hui,Cai, Qian,Ma, Dawei
, p. 5164 - 5173 (2005)
CuI-catalyzed coupling reaction of electron-deficient aryl iodides with aliphatic primary amines occurs at 40 °C under the promotion of N-methylglycine. Using L-proline as the promoter, coupling reaction of aryl iodides or aryl bromides with aliphatic primary amines, aliphatic cyclic secondary amines, or electron-rich primary arylamines proceeds at 60-90 °C; an intramolecular coupling reaction between aryl chloride and primary amine moieties gives indoline at 70 °C; coupling reaction of aryl iodides with indole, pyrrole, carbazole, imidazole, or pyrazole can be carried out at 75-90 °C; and coupling reaction of electron-deficient aryl bromides with imidazole or pyrazole occurs at 60-90 °C to provide the corresponding N-aryl products in good to excellent yields. In addition, N,N-dimethylglycine promotes the coupling reaction of electron-rich aryl bromides with imidazole or pyrazole to afford the corresponding N-aryl imidazoles or pyrazoles at 110 °C. The possible action of amino acids in these coupling reactions is discussed.
Tuning the Copper(II)/Copper(I) Redox Potential for More Robust Copper-Catalyzed C–N Bond Forming Reactions
Biswas, Saborni,Cope, James D.,Emerson, Joseph P.,Goel, Ekta,Hall, Ruby S.,Hendrich, Michael P.,Riley, Kathleen M.,Stokes, Sean L.,Valle, Henry U.,Wipf, David O.
, (2020)
Complexes of copper and 1,10-phenanthroline have been utilized for organic transformations over the last 50 years. In many cases these systems are impacted by reaction conditions and perform best under an inert atmosphere. Here we explore the role the 1,1
Two-dimensional copper-based metal-organic framework as a robust heterogeneous catalyst for the N-arylation of imidazole with arylboronic acids
Li, Zhao-Hao,Xue, Li-Ping,Wang, Lei,Zhang, Shuai-Tao,Zhao, Bang-Tun
, p. 119 - 121 (2013)
N-arylation of imidazole was accomplished with a two-dimensional (2D) [Cu(ima)2]n metal-organic framework in methanol at room temperature. A variety of N-arylimidazoles were isolated in good yields after a short reaction time. Moreov
Synthesis, structure and stability of new PtII-bis(N- heterocyclic carbene) complexes
Ahrens, Sebastian,Herdtweck, Eberhardt,Goutal, Sigrid,Strassner, Thomas
, p. 1268 - 1274 (2006)
The use of metal acetates has allowed the synthesis of NHC complexes without isolation of the free carbene. This route is very useful in cases where the metal acetates are readily available and has been used, for example, for the synthesis of bis(N-hetero
Synergistic catalysis for light-driven proton reduction using a polyoxometalate-based Cu-Ni heterometallic-organic framework
Sun, Wenlong,He, Cheng,Liu, Tao,Duan, Chunying
, p. 3805 - 3808 (2019)
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.
Efficient use of a surfactant for copper-catalyzed coupling reaction of arylboronic acids with imidazoles in water
Inamoto, Kiyofumi,Nozawa, Kanako,Kadokawa, Jun,Kondo, Yoshinori
, p. 7794 - 7798 (2012)
Copper-catalyzed oxidative coupling of arylboronic acids with imidazoles in water was realized by using an amphiphilic surfactant. By choosing an appropriate surfactant, reactions of a variety of arylboronic acids proceeded smoothly under mild and base-fr
The [Cu(OH).TMEDA]2Cl2-catalyzed coupling of arylboronic acids with imidazoles in water.
Collman,Zhong,Zeng,Costanzo
, p. 1528 - 1531 (2001)
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L-Proline Promoted Ullmann-Type Coupling Reactions of Aryl Iodides with Indoles, Pyrroles, Imidazoles or Pyrazoles
Ma, Dawei,Cai, Qian
, p. 128 - 130 (2004)
The Ullmann-type coupling reactions of aryl iodides and several nitrogen heterocycles occur at 80-90°C with L-proline as additive, giving N-arylpyrroles, N-arylindoles, N-arylimidazoles, and N-pyrazoles in good to excellent yields.
Copper-catalyzed arylation of nitrogen heterocycles from anilines under ligand-free conditions
Toummini, Dounia,Tlili, Anis,Bergs, Julien,Ouazzani, Fouad,Taillefer, Marc
, p. 14619 - 14623 (2014)
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.
Highly-efficient N-arylation of imidazole catalyzed by Cu(II) complexes with quaternary ammonium-functionalized 2-acetylpyridine acylhydrazone
Milenkovi?, Milica R.,Papastavrou, Argyro T.,Radanovi?, Du?anka,Pevec, Andrej,Jagli?i?, Zvonko,Zlatar, Matija,Gruden, Maja,Vougioukalakis, Georgios C.,Turel, Iztok,An?elkovi?, Katarina,?obelji?, Bo?idar
, p. 22 - 30 (2019)
The reaction of (E)-N,N,N-trimethyl-2-oxo-2-(2-(1-(pyridin-2-yl)ethylidene)hydrazinyl)ethan-1-aminium-chloride (HLCl) with copper(II) perchlorate led to mononuclear [CuLCl]ClO4 complex (1). The same reaction with excess of sodium azide gives di
Highly efficient and mild copper-catalyzed N- and C-arylations with aryl bromides and iodides
Cristau, Henri-Jean,Cellier, Pascal P.,Spindler, Jean-Francis,Taillefer, Marc
, p. 5607 - 5622 (2004)
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.
A novel two-dimensional metal-organic framework as a recyclable heterogeneous catalyst for the dehydrogenative oxidation of alcohol and theN-arylation of azole compounds
Liu, Chengxin,Cui, Jin,Wang, Yufang,Zhang, Mingjie
, p. 11739 - 11744 (2021)
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.
An efficient polymer-supported copper(II) catalyst for the N-arylation reaction of N(H)-heterocycles with aryl halides as well as arylboronic acids
Islam, Manirul,Mondal, Sanchita,Mondal, Paramita,Roy, Anupam Singha,Tuhina, Kazi,Salam, Noor,Paul, Sumantra,Hossain, Dildar,Mobarok, Manir
, p. 447 - 458 (2011)
Immobilization of copper onto polystyrene provided a polymer-supported copper(II) catalyst, which was effective in cross-coupling reactions between N-containing substrates and arylboronic acids using methanol as a solvent in air under base-free conditions
Copper fluorapatite catalyzed N-arylation of heterocycles with bromo and iodoarenes
Lakshmi Kantam,Venkanna,Sridhar,Shiva Kumar
, p. 3897 - 3899 (2006)
Copper exchanged fluorapatite (CuFAP) is an effective heterogeneous catalyst for N-arylation of heterocycles with bromo- or iodoarenes using K2CO3 as base. N-Arylated products were isolated in good to excellent yields, demonstrating the versatility of the reaction.
Chan–Lam cross-coupling reactions promoted by anionic copper(I)/iodide species with cationic methyl-((pyridinyl)-pyrazolyl)pyridin-1-ium
Xue, Jiang-Yan,Li, Jun-Chi,Li, Hong-Xi,Li, Hai-Yan,Lang, Jian-Ping
, p. 7014 - 7020 (2016)
Four anionic ligands including 1-methyl-3(or 4)-(1-(pyridin-2-yl)-1H-pyrazol-3-yl)pyridin-1-ium iodide ([3,2′-pypzpym]I, [4,2′-pypzpym]I) and 1-methyl-3(or 4)-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)pyridin-1-ium iodide ([2,3′-pypzpym]I, [2,4′-pypzpym]I) are prepared. Reaction of CuI with [3,2′-pypzpym]I affords a mononuclear complex [CuI2(3,2′-pypzpym)] (1) and a one-dimensional coordination polymer [(Cu4I6)(3,2′-pypzpym)2]n(2). Analogous reactions of CuI with [4,2′-pypzpym]I, [2,3′-pypzpym]I or [2,4′-pypzpym]I yield [Cu4I6(4,2′-pypzpym)2] (3), [CuI2(2,3′-pypzpym)] (4) and [CuI2(2,4′-pypzpym)] (5), respectively. Relative to that of CuI, complexes 1–5 exhibit enhanced catalytic activities towards the Chan–Lam cross-coupling reactions of imidazole and arylboronic acids in a H2O[sbnd]MeCN (v/v=2:1). This catalytic system is involved in the C[sbnd]N cross-coupling reaction and works for a variety of imidazole derivatives as well as arylboronic acids with different electronic properties.
Efficient and recyclable copper-based MOF-catalyzed N-arylation of N-containing heterocycles with aryliodides
Li, Zihao,Meng, Fei,Zhang, Jie,Xie, Jianwei,Dai, Bin
, p. 10861 - 10865 (2016)
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.
A reusable polymer supported copper(I) complex for the C-N bond cross-coupling reaction
Islam,Mondal, Sanchita,Mondal, Paramita,Roy, Anupam Singha,Tuhina, Kazi,Mobarok, Manir
, p. 1352 - 1357 (2011)
The Ullmann coupling of amines with aryl iodide as well as arylboronic acids and N(H)-heterocycles with arylboronic acids has been carried out efficiently using PS-LCu(I) catalyst. The copper complex has been prepared and characterized by using scanning electron microscope (SEM), elemental analysis, atomic absorption spectroscopy (AAS), Thermo gravimetric analysis and spectrometric methods like Fourier transform infrared spectroscopy (FTIR). The effects of various parameters such as temperature, solvent and base on the reaction system were studied. The reusability experiments show that the catalyst can be used five times without much loss in the catalytic activity.
Dendrimer-encapsulated Cu(Π) nanoparticles immobilized on superparamagnetic Fe3O4@SiO2 nanoparticles as a novel recyclable catalyst for N-arylation of nitrogen heterocycles and green synthesis of 5-substituted 1H-tetrazoles
Esmaeilpour, Mohsen,Sardarian, Ali Reza,Firouzabadi, Habib
, (2018)
In this study, dendrimer-encapsulated Cu(Π) nanoparticles immobilized on superparamagnetic Fe3O4@SiO2 nanoparticles were prepared via a multistep-synthesis. Then, the synthesized composite was fully characterized by various techniques such as fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), dynamic light scattering (DLS), UV-vis spectroscopy, energy dispersive X-ray analysis (EDX), thermogravimetric analysis (TGA) and vibration sample magnetometer (VSM). From the information gained by. FE-SEM and TEM studies it can be inferred that the particles are mostly spherical in shape and have an average size of 50?nm. Also, the amount of Cu is determined to be 0.51?mmol/g in the catalyst by inductively coupled plasma (ICP) analyzer. This magnetic nano-compound has been successfully applied as a highly efficient, magnetically recoverable and stable catalyst for N-arylation of nitrogen heterocycles with aryl halides (I, Br) and arylboronic acids without using external ligands or additives. The catalyst was also employed in a one-pot, three-component reaction for the efficient and green synthesis of 5-substituted 1H-tetrazoles using various aldehydes, hydroxylamine hydrochloride and sodium azide in water. The magnetic catalyst can be easily separated by an external magnet bar and is recycled seven times without significant loss of its activity.
A simple and efficient catalytic system for N-arylation of imidazoles in water
Wang, Yi,Wu, Zhiqing,Wang, Lixia,Li, Zhengkai,Zhou, Xiangge
, p. 8971 - 8974 (2009)
A study was conducted to develop a simple and efficient catalytic system for N-arylation of immidazoles in water. Demonstrations revealed that the catalytic system contained a number of significant advantages. Some of these advantages included the use of water as a green solvent in place of volatile organic solvents and the catalysis was performed without an inert gas atmosphere and with low catalyst loading. Investigations revealed that the presence of catalyst and PTC were essential for the catalysis reaction. The scope of aryl halide substrates was investigated by using the catalytic system under the optimized reaction conditions. It was also demonstrated that the catalytic system tolerated a variety of functionalized aryl halides in the reaction, including nitrile, nitro, acetyl, and ether groups. The new catalytic system was applied to a variety of imidazole derivatives to expand the scope of the methodology.
Nano-magnetic Fe3O4@TiO2/Cu2O composite: a simple, effective and reusable heterogeneous catalyst for ligand-free N-arylation of amines and nitrogen heterocycles
Nemati, Firouzeh,Elhampour, Ali
, p. 7611 - 7624 (2016)
Abstract: A practical and mild synthetic strategy has been investigated for the arylation of aromatic amines and nitrogen heterocycles using nano-magnetic-Fe3O4@TiO2/Cu2O composite and KOH as the base. The protocol does not require the use of expensive ligands. Notably, the catalyst is easily recoverable and reused by magnetic separation up to five runs without appreciable loss of catalytic activity. Graphical Abstract: [Figure not available: see fulltext.]
A facile and efficient oxalyldihydrazide/ketone-promoted copper-catalyzed amination of aryl halides in water
Zhu, Xinhai,Su, Li,Huang, Liye,Chen, Gong,Wang, Jinlong,Song, Huacan,Wan, Yiqian
, p. 635 - 642 (2009)
A novel three-component catalyst CuO/oxalyldihydrazide/hexane-2,5-dione was a very convenient, economic, and effective catalytic system for the Ullmann-type C-N coupling reaction in water. Both aryl bromides and aryl iodides could be aminated by a variety of amines even at room temperature or with heating to afford very good isolated yields.
Ligand-free copper(I) catalyzed N- and O-arylation of aryl halides
Sperotto, Elena,de Vries, Johannes G.,van Klink, Gerard P.M.,van Koten, Gerard
, p. 7366 - 7370 (2007)
A simple and industrially viable protocol for C-N and C-O coupling is reported here. Arylation of phenol, benzylamine and imidazole with aryl bromides is achieved using ligand-free Cu(I) halide salts in low catalytic amount (2.5 mol %).
Cu2O/nano-CuFe2O4: An efficient and magnetically recoverable catalyst for the ligand-free N-arylation of amines and nitrogen heterocycles with aryl halides
Elhampour, Ali,Nemati, Firouzeh,Kaveh, Mahdieh
, p. 223 - 225 (2016)
An efficient strategy has been developed for the N-arylation of azoles and aliphatic amines with aryl halide using a Cu2O/nano-CuFe2O4 magnetic composite as the catalyst and KOH as the base. The methodology is found to be applicable to a variety of nitrogen-containing heterocycles, such as imidazole, indole, and pyrrole, as well as aliphatic amines in high yields with practical simplicity under cost-effective "ligand-free" conditions. The magnetic property of the catalyst allowed its fast separation from the reaction medium by an external magnet. Additionally, the inexpensive catalyst could be recycled for five consecutive runs with small drops in catalytic activity.
Direct N-arylation of azaheterocycles with aryl halides under ligand-free condition
Yang, Qichao,Wang, Yufang,Zhang, Baoji,Zhang, Mingjie
, p. 2389 - 2393,5 (2012)
A simple and efficient Ci￡N cross-coupling method of aryl halides with various heterocycles was reported, by using 10 mol% of CuI as catalyst and 1.2 equiv. NaH as base. Aryl iodides, aryl bromides and many substituted aryl chlorides could efficiently react with heterocycles, providing variety of N-arylated products in good to excellent yields. The ligand-free catalyst system was stable in air and could be readily reused. An efficient, convenient and applicable method was developed for the N-arylation of azaheterocycles catalyzed by CuI and NaH under ligand free condition. Copyright
2-Aminopyrimidine-4,6-diol as an efficient ligand for solvent-free copper-catalyzed N-arylations of imidazoles with aryl and heteroaryl halides
Xie, Ye-Xiang,Pi, Shao-Feng,Wang, Jian,Yin, Du-Lin,Li, Jin-Heng
, p. 8324 - 8327 (2006)
Efficient and solvent-free copper-catalyzed N-arylations of imidazoles with aryl and heteroaryl halides have been demonstrated. In the presence of CuBr, 2-aminopyrimidine-4,6-diol, and TBAF (n-Bu4NF), a variety of imidazoles underwent the N-arylation reaction with aryl and heteroaryl halides smoothly in moderate to excellent yields. Noteworthy is that the reaction is conducted under solvent-free conditions.
Reduction system “vitamin C/glycerol” promoted copper(II)-catalyzed N-arylation
Cui, Chunna,Liu, Xiuping,Sun, Yijia,Wang, Peng,Wu, Fengtian,Wu, Ling,Yan, Fangming,Zeng, Rong,Zhang, Caihong
, (2022/02/17)
The common access to forming C-N bond is the copper-catalyzed Ullmann-type reaction. The relatively expensive and easily oxidized copper(I) is usually used in the reaction. Our group discovered that the “vitamin C/glycerol” reduction system could convert cheap and stable CuO to active low valence state copper species, as measured via X-ray photoelectron spectroscopy (XPS), to promote the C-N coupling reaction. In particular, 2-phenylindole, pyrrolo[1,2-a]quinoxaline, 1,2,4-triazole and 4-amino-7H-pyrrolo[2,3-d]pyrimidine derivative were obtained in the presence of CuO and reduction system “vitamin C/glycerol.” This method provided a simple and cost-effective approach to the preparation of N-arylation products.
Cu(OAc)2-porphyrins as an efficient catalytic system for base-free, nature mimicking Chan–Lam coupling in water
Venkateswarlu, Katta,Rao, Kanusu Umamaheswara
, (2021/03/03)
The use of porphyrins as ligands in organic synthesis reveals the natural process, because these are the constituent motifs of catalysts in many bio-organic reactions. This article presents the synthesis of two N-pincer tetradentate porphyrins; tetrasodium meso-tetra(p-sulfonatophenyl)phorphyrin (H2TSTpSPP) and meso-tetra(m-carboxyphenyl)porphyrin (H2TmCPP), and study on their aptness for Cu-catalyzed C–N coupling reactions of arylboronic acids and amines (Chan–Lam coupling reaction) in water under external base free conditions. The porphyrins and Chan–Lam coupling products were well characterized by their spectral analysis. The high product yields, application of nature-inspired conditions, large extent of substrates, ease of making and handling the ligands, avoidance of base, and use of water as reaction media are the attractive attributes of this finding.
L-Proline N-oxide dihydrazides as an efficient ligand for cross-coupling reactions of aryl iodides and bromides with amines and phenols
Ding, Zhiqiang,Nie, Nan,Chen, Tian,Meng, Lingxin,Wang, Gongshu,Chen, Zhangpei,Hu, Jianshe
supporting information, (2020/12/21)
A novel catalytic system based on L-proline N-oxide/CuI was developed and applied to the cross-coupling reactions of various N- and O- nucleophilic reagents with aryl iodides and bromides. This strategy featured in the employment of an-proline derived dihydrazides N-oxide compound as the superior supporting ligand. By using this protocol, a variety of products, including N-arylimidazoles, N-arylpyrazoles, N-arylpyrroles, N-arylamines, and aryl ethers, were synthesized with up to 99% yield.
