10040-93-4Relevant articles and documents
Bis(μ-iodo)bis((-)-sparteine)dicopper(I): versatile catalyst for direct N-arylation of diverse nitrogen heterocycles with haloarenes
Maheswaran,Krishna, G. Gopi,Prasanth, K. Leon,Srinivas,Chaitanya, G. Krishna,Bhanuprakash
, p. 2471 - 2479 (2008)
The easy-to-prepare dimeric bis(μ-iodo)bis((-)-sparteine)dicopper(I) complex is shown to be a versatile catalyst for N-arylation of number of NH-heterocycles with structurally divergent aryl halides including activated aryl chloride substrates under mild conditions. The DFT studies not only provide structural insights into square-pyramidal Cu(III) intermediate complexes derived from (-)-sparteine, but also highlight the important role of sterically demanding (-)-sparteine ligand framework in promoting activation of aryl-chlorine bonds for N-arylation of imidazoles.
Open-air N-arylation of N-H heterocycles with arylboronic acids catalyzed by copper(II) Schiff base complexes
Islam,Dey, Ram Chandra,Roy, Anupam Singha,Paul, Sumantra,Mondal, Sanchita
, p. 961 - 969 (2014)
Two copper Schiff base complexes, in both homogeneous and heterogeneous forms, were prepared and characterized by using elemental analysis, FTIR, UV-Vis spectroscopy and scanning electron microscopy. The catalytic performances of these complexes were studied in the N-arylation of N-H heterocycles with arylboronic acids in methanol without any added base at 40 °C under open air. The effects of various parameters such as solvent and temperature on the reaction system were studied. The reaction is applicable to a wide variety of N-H heterocycles and arylboronic acids. The heterogeneous catalyst was recovered by simple filtration, and reusability experiments showed that this catalyst can be used five times without much loss in the catalytic activity.
Cross coupling of arylboronic acids with imidazoles by sulfonatocopper(II) (salen) complex in water
Wang, Lixia,Jiang, Zhaoqiong,Yu, Lintao,Li, Lili,Li, Zhengkai,Zhou, Xiangge
, p. 764 - 765 (2010)
A mild and clean protocol for the cross coupling reactions between imidazoles and arylboronic acids has been developed in good to excellent yields up to 98% in the presence of sulfonatocopper(II)(salen) catalyst in water without addition of other additives and bases.
Copper(I) 3-methylsalicylate mediates the Chan-Lam N-arylation of heterocycles
Farahat, Abdelbasset A.,Boykin, David W.
, p. 245 - 252 (2015)
Copper(I) 3-methylsalicylate (CuMeSal) mediates N-arylation reactions between aryl boronic acids and aromatic heterocycles (Chan-Lam coupling) under moderate reaction conditions (K2CO3, methanol, 65 °C, in air, 3-5 h). Both electron-rich and electron-deficient aryl boronic acids and a diverse set of N-heterocycles were allowed to react and gave N-arylation products in reasonable yields, which demonstrate the utility of this catalyst.
Benzotriazole: an excellent ligand for Cu-catalyzed N-arylation of imidazoles with aryl and heteroaryl halides
Verma, Akhilesh Kumar,Singh, Jaspal,Sankar, V. Kasi,Chaudhary, Ritu,Chandra, Ramesh
, p. 4207 - 4210 (2007)
Benzotriazole (BtH) is an efficient ligand for the Cu-catalyzed N-arylation of imidazoles with aryl and heteroaryl halides. A combination of CuI/BtH was found to be an efficient and inexpensive catalyst system to carry out the N-arylation of imidazoles affording the corresponding products in good to excellent yields.
Copper-catalyzed C-N bond formation with N-heterocycles and aryl halides
Boswell, Mikki G.,Yeung, Fanny G.,Wolf, Christian
, p. 1240 - 1244 (2012)
The microwave-assisted, cuprous oxide catalyzed coupling of aryl bromides and iodides with imidazole, benzimidazole, pyrazole, or triazole was found to give a wide range of N-aryl heteroaromatic products in good to high yields. Aryl dibromides undergo sel
Expanding the Electrochemical Window: New Tunable Aryl Alkyl Ionic Liquids (TAAILs) with Dicyanamide Anions
Lerch, Swantje,Strassner, Thomas
, p. 16251 - 16256 (2019)
A set of new tunable aryl alkyl ionic liquids (TAAILs) based on the 1-aryl-3-alkyl imidazolium motif has been synthesized, in which the following variables were systematically changed: alkyl chain length, aryl substitution (group and position), and counte
Methoxyaryl substituted palladium bis-NHC complexes - Synthesis and electronic effects
Munz, Dominik,Allolio, Christoph,D?ring, Katrin,Poethig, Alexander,Doert, Thomas,Lang, Heinrich,Stra?ner, Thomas
, p. 204 - 210 (2012)
A series of methoxyphenyl substituted chelated bis-N-heterocyclic carbene palladium(II) complexes has been synthesized and characterized by cyclovoltammetry, spectroscopy (NMR, IR), solid state structures and investigated by quantum chemical calculations.
Cu-doped CoFe2O4 nanoparticles as magnetically recoverable catalyst for C–N cross-coupling reaction
Dutta, Mintu Maan,Phukan, Prodeep
, p. 38 - 42 (2018)
A new hybrid catalyst has been developed by immobilizing copper acetate onto surface of cobalt ferrite magnetic nanoparticles bearing N–O chelating ligand. The magnetic core of the catalyst was synthesized via ultrasound assisted co-precipitation method and characterized by FT-IR, XRD, EDX, SEM, TEM, TGA and VSM analysis. The catalyst was found to be very active for C–N bond forming reaction. Coupling of amines and aryl boronic acid could be achieved in high yield in methanol in presence of triethylamine at room temperature. After completion of the reaction the catalyst could be recovered using an external magnet and reused for consecutive catalytic cycles without significant decrease in the catalytic activity.
Model studies of the histidine-tyrosine cross-link in cytochrome c oxidase reveal the flexible substituent effect of the imidazole moiety
Pratt, Derek A.,Pesavento, Russell P.,Van Der Donk, Wilfred A.
, p. 2735 - 2738 (2005)
(Chemical Equation Presented) Experimental and theoretical studies were carried out to interrogate the effect of an imidazole substituent in each of the ortho, meta, and para positions on the pKa, E°, and O-H BDE of phenol. The results reveal t
Formation of N-Heterocyclic Carbenes by Tautomerization of Mesomeric Betaines: Cyclic Boron Adducts and Palladium Complexes from 2-(Imidazolium-1-yl)phenolates
Liu, Ming,Nieger, Martin,Hübner, Eike G.,Schmidt, Andreas
, p. 5416 - 5424 (2016)
2-(Imidazolium-1-yl)phenolates are conjugated heterocyclic mesomeric betaines in tautomeric equilibrium with the corresponding N-heterocyclic carbenes (NHCs), 3-(2-hydroxyphenyl)-imidazol-2-ylidenes. The carbene tautomers can be trapped as thiones (X-ray analysis). Moreover, bis(triphenylphosphine)palladium(II) dichloride in THF trapped the carbene tautomer as a palladium complex without participation of the phenolate group (X-ray analysis). The corresponding anionic NHCs, 2-phenolate-substituted imidazol-2-ylidenes, can be trapped by triethylborane or triphenylborane to form 4,4-diethyl- or 4,4-diphenyl-4H-benzo[e]imidazo[2,1-c][1,4,2]oxaza-borininium-4-ides, respectively (two X-ray analyses). These tricyclic systems are the first representatives of a new heterocyclic ring system. The results of DFT calculations concerning the HOMO/LUMO profiles and partial charges are also presented.
Efficient Ullmann C-X coupling reaction catalyzed by a recoverable functionalized-chitosan supported copper complex
Liu, Xuemin,Chang, Shuo,Chen, Xinzhi,Ge, Xin,Qian, Chao
, p. 16013 - 16020 (2018)
Three different types of functionalized-CS were prepared and anchored with copper salts for use as the catalyst for the Ullmann C-X coupling reaction. The Schiff-basic chitosan supported copper complex (PCCS@CuI) exhibits the highest catalytic activity. The structure of the catalyst was characterized by FTIR spectroscopy, TG, XRD, SEM, EDS and XPS. This catalyst exhibited high applicability for the C-N and C-S coupling reactions, in which good to excellent yields were obtained. Its easy separation, good reusability and stability were notable.
Palladium(II) 9,10-phenanthrenequinone N-substituted thiosemicarbazone/semicarbazone complexes as efficient catalysts for N-arylation of imidazole
Anitha, Panneerselvam,Manikandan, Rajendran,Viswanathamurthi, Periasamy
, p. 3537 - 3550 (2015)
A series of palladium complexes, [PdCl(L1-4)] (1-4) (L1 = 9,10-phenanthrenequinone thiosemicarbazone, L2 = 9,10-phenanthrenequinone methylthiosemicarbazone, L3 = 9,10-phenanthrenequinone phenylthiosemicarbazone, and L4 = 9,10-phenanthrenequinone semicarbazone), have been synthesized and characterized by elemental analyses, UV-vis, FT-IR, 1H and 13C NMR, and ESI-Mass spectroscopic methods. The catalytic efficiency of the synthesized complexes was examined against N-arylation of imidazole. The system works well with the electron-rich, -neutral, and -deficient aryl halides to afford the products in good to excellent yields. Sterically congested aryl halides and heteroaryl halides have also been used as substrates to provide N-arylated heterocycles. In addition, this methodology can be applicable to other substrates with N-containing heterocycles.
Efficient copper-catalyzed N-arylation of amides and imidazoles with aryl iodides
Ali, Md. Ashif,Saha, Prasenjit,Punniyamurthy, Tharmalingam
, p. 908 - 910 (2010)
The C-N cross-coupling of amides and imidazoles with aryl iodides is described using CuI in tetrabutylammonium bromide (TBAB) under ligand-free conditions. The reaction is simple, general, and efficient affording the C-N cross-coupled products in shorter time and in high yield. Georg Thieme Verlag Stuttgart ? New York.
A concept of supported amino acid ionic liquids and their application in metal scavenging and heterogeneous catalysis
Chen, Wen,Zhang, Yuanyuan,Zhu, Liangbo,Lan, Jingbo,Xie, Rugang,You, Jingsong
, p. 13879 - 13886 (2007)
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.
Chan-Lam-Type C-N Cross-Coupling Reactions under Base- and Ligand-Free CuI-Zeolite Catalysis
Garnier, Tony,Sakly, Randa,Danel, Mathieu,Chassaing, Stefan,Pale, Patrick
, p. 1223 - 1230 (2017)
Various representative copper(I)-exchanged zeolites were investigated for their catalytic potential in Chan-Lam cross-coupling reactions. CuI-USY appeared as the best catalyst and proved to efficiently promote C-N cross-coupling processes under attractive, simple, and practical conditions, namely refluxing in methanol under air and without any base.
Ninhydrin: an efficient ligand for the Cu-catalyzed N-arylation of nitrogen-containing heterocycles with aryl halides
Huang, Yi-Zheng,Gao, Jin,Ma, Hong,Miao, Hong,Xu, Jie
, p. 948 - 951 (2008)
Cu2O/ninhydrin was found to be an efficient catalyst system for the N-arylation of nitrogen-containing heterocycles with aryl and heteroaryl iodides, bromides and even unactivated chlorides to give the products in moderate to excellent yields.
A green, homogeneous and reusable surfactant/copper based ionic liquid for the N-arylation of indoles, pyrazoles and imidazoles
Heidarizadeh, Fariba,Majdi-Nasab, Afrooz
, p. 6360 - 6363 (2015)
An efficient surfactant/copper based ionic liquid promoter was examined as a reusable system for the N-arylation of indole, pyrazole and imidazole by a variety of aryl halides. The products were obtained in good to excellent yields by a convenient one-pot procedure. The reaction could be carried out in water under air and did not require the use of arylboronic acids as the active aryl source, palladium as the catalyst or a strong base.
Highly efficient copper-catalyzed N-arylation of nitrogen-containing heterocycles with aryl and heteroaryl halides
Zhu, Liangbo,Cheng, Liang,Zhang, Yuxi,Xie, Rugang,You, Jingsong
, p. 2737 - 2743 (2007)
(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.
Correction to: Polyfunctional Imidazolium Aryloxide Betaine/Lewis Acid Catalysts as Tools for the Asymmetric Synthesis of Disfavored Diastereomers (Journal of the American Chemical Society (2019) 141 (12029-12043) DOI: 10.1021/jacs.9b04902)
Willig, Felix,Lang, Johannes,Hans, Andreas C.,Ringenberg, Mark R.,Pfeffer, Daniel,Frey, Wolfgang,Peters, René
, p. 17022 - 17022 (2019)
Page 12035 and Supporting Information pp S91-S94. It has come to our attention that the wrong initial concentration of 1a was erroneously used in two experiments of the "same excess" protocol.1 The experiments were thus repeated (0.055 rather than 0.06 mol/L of 1a was erroneously used before), and an excellent overlay of the "time-adjusted same excess" reaction profiles and the standard reaction profile, as previously presented, was found. This indicates that no significant catalyst deactivation takes place and that the active catalyst concentration remains constant during the catalytic reaction. The conclusions are thus not affected by the unintentional error. The corrected Figure 1 is shown below, and a corrected including Figures S1-S28 and Tables S1-S8 (corrected).(Figure Persented).Supporting Information file is available, in which pp S91?S94 have been replaced, in which the correct kinetic experiments are described, including raw data. We apologize for any inconvenience.
Synthesis and Physical Properties of Tunable Aryl Alkyl Ionic Liquids (TAAILs)
Lerch, Swantje,Strassner, Thomas
supporting information, p. 15554 - 15557 (2021/10/06)
Tunable aryl alkyl ionic liquids (TAAILs) based on the imidazolium cation were first reported in 2009. Since then, a series of TAAILs with different properties due to the electron-donating or -withdrawing effect of the substituents at the aryl ring has be
