- N-ARYLATION OF AZOLES AND THEIR BENZO DERIVATIVES BY p-TOLYLLEAD TRIACETATE
-
The N-arylation of a variety of azoles and their benzo derivatives was achieved by treatment at 90-100 deg c with p-tolyllead triacetate in the presence of copper (II) acetate.
- Lopez-Alvarado, Pilar,Avendano, Carmen,Menendez, J. Carlos
-
-
Read Online
- Synthesis and characterization of nano-cellulose immobilized phenanthroline-copper (I) complex as a recyclable and efficient catalyst for preparation of diaryl ethers, N-aryl amides and N-aryl heterocycles
-
Functionalized nanocellulose was prepared and employed for immobilization of phenanthroline-copper(I) complex to afford cellulose nanofibril grafted heterogeneous copper catalyst [CNF-phen-Cu(I)]. This nanocatalyst was well characterized using FT-IR, NMR, XRD, CHNS, AAS, TGA, EDX and SEM. The activities of the synthesized catalyst were examined in the synthesis of diaryl ethers via C-O cross-coupling of phenols and aryl iodides, as well as, the preparation of N-aryl amides and N-aryl heterocycles through C-N cross-coupling of amides and N-H heterocycle compounds with aryl halides. In this trend, various substrates containing electron-donating and electron-withdrawing groups were exploited to evaluate the generality of this catalytic protocol. Accordingly, the catalyst demonstrated remarkable catalytic efficiency for both C-N and C-O cross-coupling reactions, thereby resulting in good to excellent yields of the desired products. Furthermore, the recoverability experiments of the catalyst showed that it can be readily retrieved by simple filtration and successfully reused several times with negligible loss of its catalytic activity.
- Aghili, Nora,Hosseinzadeh, Rahman,Mavvaji, Mohammad
-
-
- Copper pyrithione (CuPT)-catalyzed/mediated amination and thioarylation of (hetero)aryl halides: A competition
-
A facile method for the synthesis of N-arylheterocycles and di(hetero)aryl sulfides under mild condition is described. In these transformations, copper pyrithione (CuPT) was used as the copper catalyst for C─N coupling, while served as catalyst and coupled partner for C─S coupling with high yields and broad substrate tolerance. The S-arylation process was also utilized for the construction of valuable bioactive 2-sulfonylpyridine 1-oxide derivatives.
- Cao, Ningtao,Song, Bao,Xie, Jianwei,Zhang, Jie
-
-
- A post-synthetically modified metal-organic framework for copper catalyzed denitrative C-N coupling of nitroarenes under heterogeneous conditions
-
Here we report, for the first time, the Ullmann C-N coupling reaction of nitroarenes which is achieved by using a copper containing metal-organic framework (MOF) catalyst under heterogenous conditions. The ready availability of nitroarenes and their low cost have made them ideal replacements for haloarenes as electrophilic coupling partners. Notably, the reaction protocol suppresses the by-product formation in the catalytic reaction. The catalyst has been designed and synthesized by two step post-synthesis functionalization of a MOF,viz.dabco MOF-1 with a -NH2functional group (DMOF-NH2). In the post-synthetic treatment, salicylaldehyde has been used for organic modification first and then copper(ii) was successfully incorporated onto the inner surface of the porous material. The hybrid porous solid thus obtained has been employed in the catalytic C-N coupling reaction of nitroarenes with a wide variety of amines under heterogeneous conditions, which displayed very high turnover frequencies (TOF) in catalytic reactions attesting its efficacy towards theN-arylation reaction.
- Maity, Tanmoy,Ghosh, Pameli,Das, Soma,Saha, Debraj,Koner, Subratanath
-
p. 5568 - 5575
(2021/04/06)
-
- 2 - Alkynyl mannose derivative and application thereof
-
The present invention relates to a 2-alkynyl mannose derivative and an application thereof. The mannose derivative, as well as a pharmaceutically acceptable salt, an isotope and an isomer thereof have the structure represented by general formula I. The de
- -
-
Paragraph 0102-0106
(2021/10/05)
-
- A Highly Active, Recyclable and Cost-Effective Magnetic Nanoparticles Supported Copper Catalyst for N-arylation Reaction
-
Abstract: The immobilization of a copper complex by covalent anchoring of 2-hydroxybenzophenone on the surface of amine-functionalized magnetic nanoparticles was reported. The structure and morphology of the catalyst was characterized by different techniques such as Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron micrograph (TEM), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), vibrating sample magnetometer (VSM) and inductively coupled plasma (ICP) spectroscopy. This efficient and cost effective catalyst was applied in the N-arylation reaction and the products were obtained in good to excellent yields in short reaction times. The cost-effective catalyst demonstrated high stability, which could be facilely separated from the reaction mixture by applying an external magnet and recycled at least four times with only a slight decrease in its activity. Graphic Abstract: [Figure not available: see fulltext.]
- Zahedi, Razieh,Asadi, Zahra,Firuzabadi, Fahimeh Dehghani
-
-
- Copper quinolate: A simple and efficient catalytic complex for coupling reactions
-
We describe an effective and novel method to prepare N-aryl imidazoles via the copper quinolate-catalyzed N-arylation of aryl halides and imidazoles. A wide range of products were obtained in moderate to excellent yields under the optimal reaction conditions. Applying standard conditions, the model reaction could be performed on a gram scale. This method also presents a new avenue to the “click” reaction of terminal alkynes, benzyl bromide, and sodium azide and to the construction of C–C bonds by homocoupling of phenylboronic acid or phenylacetylene derivatives with the aid of copper quinolate.
- Wu, Fengtian,Li, Huiqin,Xie, Jianwei
-
-
- Nucleophilic aromatic substitution of unactivated fluoroarenes enabled by organic photoredox catalysis
-
Nucleophilic aromatic substitution (SNAr) is a classical reaction with well-known reactivity toward electron-poor fluoroarenes. However, electron-neutral and electron-rich fluoro(hetero)arenes are considerably underrepresented. Herein, we present a method for the nucleophilic defluorination of unactivated fluoroarenes enabled by cation radical-accelerated nucleophilic aromatic substitution. The use of organic photoredox catalysis renders this method operationally simple under mild conditions and is amenable to various nucleophile classes, including azoles, amines, and carboxylic acids. Select fluorinated heterocycles can be functionalized using this method. In addition, the late-stage functionalization of pharmaceuticals is also presented. Computational studies demonstrate that the site selectivity of the reaction is dictated by arene electronics.
- Nicewicz, David A.,Pistritto, Vincent A.,Schutzbach-Horton, Megan E.
-
supporting information
p. 17187 - 17194
(2020/11/02)
-
- SUBSTITUTED PYRAZOLE DERIVATIVES AS INSECTICIDES AND FUNGICIDES
-
An object of the present disclosure is to provide a novel substituted pyrazole compound or a salt thereof as represented by formula (1) that controls pests: wherein, Q represents an oxygen atom or a sulfur atom, or the like; R represents substituted or unsubstituted aryl, C1-C12alkyl, or the like; Represents hydrogen, substituted or unsubstituted C1- C12alkylcarbonyl, substituted or unsubstituted C1-C12alkoxycarbonyl or the like; R2and R3each independently represent hydrogen, substituted or unsubstituted C1-C12alkyl, or the like; R4and R5each independently represent hydrogen, substituted or unsubstituted C1- C12alkyl, or the like; andX1, X2and X3grepresent C-R8, C-Rg and C-R|0, respectively, wherein R8, R9and Rjgeach independently represent hydrogen, halogen, methyl, ethyl or the like. The compounds of formula (1) are useful as insecticides and fungicides.
- -
-
Page/Page column 50
(2020/01/24)
-
- Ruthenium-Catalyzed ortho- And meta-H/D Exchange of Arenes
-
Ruthenium-catalyzed aromatic H/D exchange in [D4]acetic acid has been developed. By using N-heteroarenes as directing groups, both ortho and meta positions are selectively deuterated with high levels of D incorporation. Moreover, this strategy provides an alternative way to achieve meta-C-H activation.
- Zhao, Liang-Liang,Liu, Wei,Zhang, Zengyu,Zhao, Hongyan,Wang, Qi,Yan, Xiaoyu
-
supporting information
p. 10023 - 10027
(2019/12/24)
-
- Palladium-Catalyzed C-N Cross-Coupling of NH-Heteroarenes and Quaternary Ammonium Salts via C-N Bond Cleavage
-
In this paper, we extend the substrate class of Buchwald-Hartwig amination to quaternary ammonium salts. In the presence of Pd(OAc)2 and t-BuXPhos, the coupling of aryl- or arylmethyltrimethylammonium triflates with NH-heteroarenes via C-N bond cleavage affords the desired N-aryl or N-arylmethyl heteroarenes in moderate to excellent yields.
- Chen, Hongyi,Yang, Hongqin,Li, Nutao,Xue, Xinghua,He, Ze,Zeng, Qingle
-
p. 1679 - 1685
(2019/08/20)
-
- Synthesis of n-arylpyrazoles by palladium-catalyzed coupling of aryl triflates with pyrazole derivatives
-
A method for the synthesis of N-arylpyrazoles by palladium-catalyzed coupling of aryl triflates with pyrazole derivatives is described. Using tBuBrettPhos as a ligand, the palladium-catalyzed C-N coupling of a variety of aryl triflates including ortho-substituted ones with pyrazole derivatives proceeded efficiently to give N-arylpyrazole products in high yields. 3-Trimethylsilylpyrazole was found to be an excellent pyrazole substrate for the coupling, and the corresponding product, 1-aryl-3-trimethylsilylpyrazole, also served as a great template for the syntheses of N-arylpyrazole derivatives, as demonstrated by regioselective halogenation at the 3-, 4-, and 5-positions of the pyrazole ring.
- Onodera, Shunsuke,Kochi, Takuya,Kakiuchi, Fumitoshi
-
-
- Synthesis of N-Arylpyrazoles by Palladium-Catalyzed Coupling of Aryl Triflates with Pyrazole Derivatives
-
A method for the synthesis of N-arylpyrazoles by palladium-catalyzed coupling of aryl triflates with pyrazole derivatives is described. Using tBuBrettPhos as a ligand, the palladium-catalyzed C-N coupling of a variety of aryl triflates including ortho-substituted ones with pyrazole derivatives proceeded efficiently to give N-arylpyrazole products in high yields. 3-Trimethylsilylpyrazole was found to be an excellent pyrazole substrate for the coupling, and the corresponding product, 1-aryl-3-trimethylsilylpyrazole, also served as a great template for the syntheses of N-arylpyrazole derivatives, as demonstrated by regioselective halogenation at the 3-, 4-, and 5-positions of the pyrazole ring.
- Onodera, Shunsuke,Kochi, Takuya,Kakiuchi, Fumitoshi
-
p. 6508 - 6515
(2019/05/24)
-
- Design, synthesis, and evaluation of indeno[2,1-c]pyrazolones for use as inhibitors against hypoxia-inducible factor (HIF)-1 transcriptional activity
-
HIF-1 is regarded as a promising target for the drugs used in cancer chemotherapy, and creating readily accessible templates for the development of synthetic drug candidates that could inhibit HIF-1 transcriptional activity is an important pursuit. In this study, indeno[2,1-c]pyrazolones were designed as readily available synthetic inhibitors of HIF-1 transcriptional activity. Nine compounds were synthesized in 4–5 steps from commercially available starting materials. In evaluations of the ability to inhibit the hypoxia-induced transcriptional activity of HIF-1, compound 3c showed a higher level compared with that of known inhibitor, YC-1. The compound 3c suppressed HIF-1α protein accumulation without affecting the levels of HIF-1α mRNA.
- Fuse, Shinichiro,Kadonosono, Tetsuya,Kizaka-Kondoh, Shinae,Kuchimaru, Takahiro,Nakamura, Hiroyuki,Sato, Shinichi,Suzuki, Kensuke,Ueda, Hiroki
-
supporting information
(2019/11/26)
-
- PYRAN DERVATIVES AS CYP11A1 (CYTOCHROME P450 MONOOXYGENASE 11A1) INHIBITORS
-
Compounds of formula (I) wherein R1, R2,R3,R4,R5,R23,R24,L, A and Bare as defined in claim 1, or pharmaceutically acceptable salts thereof are disclosed. The compounds of formula (I) possess utility as cytochrome P450 monooxygenase 11A1(CYP11A1) inhibitors. The compounds are useful as medicaments in the treatment of steroidreceptor, particularly androgen receptor,dependent diseases and conditions, such asprostate cancer.
- -
-
Page/Page column 75
(2018/07/29)
-
- The Catalytic Properties of a Copper-Based Nanoscale Coordination Polymer Fabricated by a Solvent-Etching Top-Down Route
-
Manipulating particle size is a powerful means of creating unprecedented applications in both inorganic and organic materials. Coordination polymers, which are emerging as a type of organic–inorganic hybrid materials, have attracted thriving interest in a variety of applications, but nanoscale coordination polymers have scarcely been touched. In this work, the pure-phase {Cu6[1,4-bis(imidazol-1-yl)butane]3I6}∞ coordination polymer with different sizes and morphologies was synthesized for the first time through a facile top-down route assisted by solvent etching. The size and morphology could be adjusted simply by varying the participating etching solvents. Our mechanistic investigations suggest that the bulk coordination polymer as a precursor in the etching solvents may experience a process of dispersion, dissolution, and recrystallization to generate the nanoscale counterpart. High catalytic activity of the nanoscale coordination polymer was observed in the N-arylation of imidazole aryl halides, and this was attributed to a high surface area and a low coordination number of unsaturated coordination sites. This simple and rapid preparation, requiring neither specialized equipment nor harsh conditions, suggests a wealth of potential for reducing the size of coordination polymers to comply with various practical applications.
- Cao, Xiaowei,Fang, Zhenlan,Huang, Wei,Ju, Qiang
-
supporting information
p. 4803 - 4807
(2017/11/14)
-
- Copper(I) Oxide/N,N′-Bis[(2-furyl)methyl]oxalamide-Catalyzed Coupling of (Hetero)aryl Halides and Nitrogen Heterocycles at Low Catalytic Loading
-
An easily prepared oxalic diamide is a powerful ligand for the copper-catalyzed coupling of aryl halides with nitrogen heterocycles. Only 1–2 mol% each of copper(I) oxide and N,N′-bis[(2-furyl)methyl]oxalamide (BFMO) are needed to form N-arylation products under mild conditions. More than 10 different types of nitrogen heterocycles are compatible with these conditions, thereby giving the corresponding N-arylation products. (Figure presented.).
- Pawar, Govind Goroba,Wu, Haibo,De, Subhadip,Ma, Dawei
-
supporting information
p. 1631 - 1636
(2017/05/22)
-
- A N - aryl pyrazole compounds and N - aryl imidazole compound of preparation method
-
The invention discloses a preparation method of an N-arylpyrazole compound and an N-arylimidazole compound. The method comprises the following steps: reacting at 20-120 DEG C for 6-48 hours by taking aryl halide and pyrazole or imidazole as substrates and copper salt as a catalyst in an organic solvent in the presence of alkali and a nitrogenous ligand under nitrogen protection; and after the reaction is finished, separating and purifying a reaction liquid to obtain the N-arylpyrazole compound or the N-arylimidazole compound. A product prepared by utilizing the method disclosed by the invention can not only be directly used, but also be used for other reactions as a substrate and has the advantages of moderation in adopted reaction condition, simple operation step and post-processing process, high yield and suitability for large-scale production.
- -
-
Paragraph 0043; 0044; 0045; 0046; 0047; 0048
(2017/10/05)
-
- Teaching Old Compounds New Tricks: DDQ-Photocatalyzed C?H Amination of Arenes with Carbamates, Urea, and N-Heterocycles
-
The C?H amination of benzene derivatives was achieved using DDQ as photocatalyst and BocNH2 as the amine source under aerobic conditions and visible light irradiation. Electron-deficient and electron-rich benzenes react as substrates with moderate to good product yields. The amine scope of the reaction comprises Boc-amine, carbamates, pyrazoles, sulfonimides and urea. Preliminary mechanistic investigations indicate arene oxidation by the triplet of DDQ to radical cations with different electrophilicity and a charge transfer complex between the amine and DDQ as intermediate of the reaction.
- Das, Somnath,Natarajan, Palani,K?nig, Burkhard
-
supporting information
p. 18161 - 18165
(2017/12/28)
-
- Ruthenium-Catalyzed meta-Selective C?H Mono- and Difluoromethylation of Arenes through ortho-Metalation Strategy
-
The first example for the ruthenium-catalyzed ligand-directed meta-selective C?H mono- and difluoromethylation is developed, affording a variety of new meta-mono- and difluoromethylated 2-phenylpyridines, 2-phenylpyrimidines, and 1-phenylpyrazoles in moderate-to-good yields. This new transformation exhibits broad substrate scope, good functional group tolerance, and high efficiency, and offers a practical approach to synthesize mono- and difluoromethylated arenes. Mechanistic studies indicate that a reaction pathway involving palladium-initiated radical species is involved in the catalytic cycle. The new dual catalytic system consisting of compatible ruthenium(II) and palladium(0) complexes enables the key processes of C?H activation and mono-/difluoromethyl-radical formation to occur and achieves the meta-selective functionalization efficiently. In addition, the present protocol can also be extended to non-fluoromethylation.
- Li, Zhong-Yuan,Li, Liang,Li, Qi-Li,Jing, Kun,Xu, Hui,Wang, Guan-Wu
-
supporting information
p. 3285 - 3290
(2017/03/16)
-
- SBA-15 Immobilized Phenanthroline-Copper(I) Complex as a Recyclable Efficient Catalyst for N-Arylation of Amides and N-H Heterocycles with Aryl Halides
-
5-(N,N-bis-3-(triethoxysilyl) propyl) ureyl-1,10-phenanthroline was prepared and successively grafted onto mesoporous silica of SBA-15 to get SBA-15 anchored ligand which was then reacted with Cu(I) to get SBA-15 anchored complex as the heterogeneous copper catalyst. This catalyst was characterized by FT-IR, XRD, CHN, AAS, TGA, EDAX, BET, SEM and TEM. The activities of the catalyst were tested in C-N cross-coupling of amides and N-H heterocycle compounds with aryl halides. The catalyst showed high catalytic activities for these cross-coupling reactions providing good to excellent yields of desired products. Moreover, the catalyst can be easily recovered by simple filtration and reused several times without significant loss of its catalytic activity.
- Hosseinzadeh, Rahman,Aghili, Nora,Tajbakhsh, Mahmood
-
p. 193 - 203
(2016/03/12)
-
- Ethylene glycol, an efficient and recoverable medium for copper-catalyzed N-arylation of diazoles under microwave irradiation
-
Ethylene glycol was used as an efficient and recoverable medium for the reaction of diazoles with aryl iodides and aryl bromides in the presence of CuCl2 as the catalyst and K2CO3 as the base. Consequently, imidazole, benzimidazole, and pyrazole reacted readily under microwave irradiation to give good to excellent yields of their corresponding N-arylated products in relatively short time periods. Apparently, ethylene glycol plays a dual role by activating the catalyst and also providing a homogenous medium for the processes. The reaction medium consisting of the solvent, the base, and the copper salt was recovered and reused successfully in the next several reactions.
- Sharifi, Ali,Ghonouei, Nima,Abaee, M. Saeed
-
supporting information
p. 249 - 256
(2016/03/09)
-
- N-Picolinamides as ligands for Ullmann-type C-N coupling reactions
-
The use of N-phenyl-2-pyridincarboxamide-1-oxide as a ligand with Cu2O in Ullmann type C-N bond formations between aryl halides and N-heteroaryls in common solvents, such as MeCN, DMF, and DMSO at 82-120 °C has been successfully demonstrated. The ligand is effective when only 4% equiv is used relative to the substrate. The reaction provided the corresponding products in coupling of electron-rich, electron poor, and ortho-substituted aryl halides, including ortho aryl-chlorides, in good to very good yields. N-arylation is selectively preferred at the benzyl position when ortho-halide benzyl bromide is reacted with one equivalent of pyrazole. However, di-N-arylation is achieved in very high yields when 2.5 equiv of pyrazole is used, providing a stoichiometric control over the coupling reaction.
- Damkaci, Fehmi,Alawaed, Abdulkhaliq,Vik, Erik
-
supporting information
p. 2197 - 2200
(2016/05/02)
-
- Pyrazolyl pyrimidinyl ether compound and use thereof
-
The present invention discloses a pyrazolyl pyrimidinyl ether compound, the compound has a structure as shown in formula (I), and the substituent groups in the (I) are as defined in the specification. The pyrazolyl pyrimidinyl ether compound has broad-spectrum bactericidal activity, has good control effects on downy mildew of cucumber, anthracnose of cucumber, rice blast, cucumber gray mold and other diseases, and is especially better in the control effect on the anthracnose of cucumber,.
- -
-
Paragraph 0364; 0365; 0366
(2016/10/08)
-
- Directing/Protecting-Group-Free Synthesis of Tetraaryl-Substituted Pyrazoles through Four Direct Arylations on an Unsubstituted Pyrazole Scaffold
-
A directing/protecting-group-free synthesis of 1,3,4,5-tetraaryl-substituted pyrazoles was achieved through four transition metal-catalyzed direct arylations. Various pyrazoles with four different aryl rings were obtained using readily available reagents from an unsubstituted pyrazole. Two aryl-substituted pyrazoles showed intense violet fluorescence, high quantum yields (Φf=0.68, 0.64), and large Stokes shifts (19000, 15200cm-1).
- Fuse, Shinichiro,Morita, Taiki,Johmoto, Kohei,Uekusa, Hidehiro,Tanaka, Hiroshi
-
supporting information
p. 14370 - 14375
(2015/10/05)
-
- Ligand-free N-arylation of heterocycles using metal-organic framework [Cu(INA)2] as an efficient heterogeneous catalyst
-
A metal-organic framework [Cu(INA)2] was synthesized and used as a heterogeneous catalyst for arylation of a wide range of N-H heterocycles and aryl halides under ligand-free conditions. The N-arylation reaction involved the use of 5 mol% Cu-MOF catalyst with K3PO4 or tBuOLi as the base in dimethylacetamide (DMA) solvent at 100 °C in 6 h. [Cu(INA)2] exhibited higher catalytic activity for the N-arylation transformation than that of common homogeneous copper catalysts and other Cu-MOFs with unsaturated open metal sites such as Cu2(BDC)2(BPY), Cu3(BTC)2, and Cu2(BDC)2(DABCO). Interestingly, reaction conditions are compatible with a wide range of N-H heterocycles, functional groups, and aryl chlorides. A leaching test indicated no contribution of leached active species in the reaction filtrate. Furthermore, the [Cu(INA)2] catalyst could be facilely separated from the reaction mixture and recovered and reused several times without a significant degradation in catalytic activity.
- Truong, Thanh,Nguyen, Chi V.,Truong, Ngoc T.,Phan, Nam T. S.
-
p. 107547 - 107556
(2016/01/09)
-
- Facile Synthesis of 1-Arylpyrazoles
-
A convenient and transition-metal-free synthesis of 1-arylpyrazoles that involves the cycloaddition of 3-arylsydnones and acrylic acid is presented. The process proceeds smoothly to obtain the target products with moderate to high yields.
- Yang, Yiwen,Kuang, Chunxiang
-
supporting information
p. 2281 - 2284
(2015/08/03)
-
- Ruthenium-catalyzed c-h silylation of 1-arylpyrazole derivatives and fluoride-mediated carboxylation: Use of two nitrogen atoms of the pyrazole Group
-
Carboxylation of 1-arylpyrazole derivatives was developed using a ruthenium-catalyzed ortho silylation in conjunction with fluoride-mediated carboxylation with carbon dioxide. The two nitrogen atoms of pyrazole play crucial roles in promoting ortho silylation via the formation of a five-membered ruthenacycle and in accelerating aryl anion formation by lowering the electron density of the aromatic ring. Georg Thieme Verlag Stuttgart New York.
- Mita, Tsuyoshi,Tanaka, Hiroyuki,Michigami, Kenichi,Sato, Yoshihiro
-
supporting information
p. 1291 - 1294
(2014/06/10)
-
- 3-(Diphenylphosphino)propanoic acid: An efficient ligand for the Cu-catalyzed N-arylation of imidazoles and 1H-pyrazole with aryl halides
-
3-(Diphenylphosphino)propanoic acid (L2) has proved to be an efficient ligand for the copper-catalyzed CN coupling reactions. N-arylation of imidazoles with aryl iodides catalyzed by CuCl/L2 was smoothly carried out in DMSO at 100 °C with a yield up to 98%. N-arylation of 1H-pyrazole with aryl iodides and bromides catalyzed by Cu(OAc)2/L2 in 1,4-dioxane also gave the corresponding products with yields of 40%-98%.
- Liu, Ya-Shuai,Liu, Yan,Ma, Xiao-Wei,Liu, Ping,Xie, Jian-Wei,Dai, Bin
-
p. 775 - 778
(2014/06/09)
-
- Copper-catalyzed arylation of nitrogen heterocycles from anilines under ligand-free conditions
-
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
-
supporting information
p. 14619 - 14623
(2015/01/09)
-
- Aromatic N-arylations catalyzed by copper-anchored porous zinc-based metal-organic framework under heterogeneous conditions
-
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
-
p. 2373 - 2383
(2014/08/18)
-
- Salen-Cu(II) complex catalysed N-arylation of pyrazole under mild conditions
-
Three inexpensive and air-/moisture-stable complexes (Salden)Cu (Salden = N, N'-bis(salicylidene)-1,2-dimethylethylenediamine), (Saldch)Cu (Saldch = N, N'-bis(salicylidene)-1,2-cyclohexenediamine), and (Salph)Cu (salph = N, N'-bis(salicylidene)-1,2-phenylenediamine) were synthesised and evaluated as catalysts for the N-arylation of pyrazole with aryl halides. A variety of aryl iodides and bromides underwent coupling with pyrazole, promoted by the (Saldch)Cu complex, in moderate to excellent yields without the protection by an inert gas.
- Liu, Yan,Liu, Wei,Zhang, Qin,Liu, Ping,Xie, Jian-Wei,Dai, Bin
-
p. 636 - 637
(2013/11/06)
-
- N-arylation of heterocycles catalyzed by activated-copper in pure water
-
N-arylation Activated-copper powder is an efficient catalyst for the N-arylation of heterocycles with aryl halides and can be reused several times. The reactions can proceed smoothly in water by using LiOH as base and give the corresponding products in good yields. The protocol shows good tolerance toward various functional groups.
- Yang, Qichao,Wang, Yufang,Lin, Dong,Zhang, Mingjie
-
supporting information
p. 1994 - 1997
(2013/04/10)
-
- N-Arylation of heterocycles promoted by tetraethylenepentamine in water
-
Tetraethylenepentamine and triethylenetetramine are found to be efficient organic bases for the N-arylation of pyrazole and imidazole with aryl and heteroaryl-iodides and -bromides catalyzed by CuI in water at moderate temperature. The cross-couplings proceed smoothly with good to excellent yields and a variety of functional groups are tolerated under this condition.
- Yang, Qichao,Wang, Yufang,Yang, Li,Zhang, Mingjie
-
supporting information
p. 6230 - 6233
(2013/07/19)
-
- Ruthenium-catalyzed C-H functionalization of arylpyrazoles: Regioselective acylation with acid chlorides
-
A ruthenium-catalyzed C-H acylation of arylpyrazoles with a variety of acyl chlorides is described. The acylation reaction exhibits good regioselectivity and both aromatic and aliphatic acyl chlorides can be effectively coupled to the arylpyrazoles at the
- Liu, Po Man,Frost, Christopher G.
-
supporting information
p. 5862 - 5865
(2013/12/04)
-
- An unusual 30-membered copper(i) cluster derived from the C-S bond cleavage and its use in heterogeneous catalysis
-
The Cu(i)-mediated C-S bond cleavage of 5-methyl-4-(p-tolyl)pyrimidine-2- thiol (mtpmtH) gave one 30-nuclear cluster [Cu30I16(mtpmt) 12(μ10-S4)], one polymeric complex [(bmtpms)Cu-(μ-I)]n and one tetranuclear complex [(bmptmds){Cu(μ-I)}2]2; the 30-nuclear cluster displayed excellent catalytic performances in the coupling reactions of N-heterocycles and arylboronic acids and could be recycled and reused.
- Li, Hong-Xi,Zhao, Wei,Li, Hai-Yan,Xu, Zhong-Lin,Wang, Wen-Xia,Lang, Jian-Ping
-
supporting information
p. 4259 - 4261
(2013/07/05)
-
- Octanuclear Cu(I)-dithiophosphates: An efficient catalyst system for N-arylation of azoles, amines, and amides
-
The formation of a C-N bond via the cross-couplings of aryl iodides with azoles, aryl amine, and amides can be successfully achieved in decent yield by the utilization of both [Cu8(H){S2P(OiPr) 2}6]+ and [Cu8{S2P(OEt) 2}6]2+ as the pre-catalysts.
- Wu, Cheng-Chieh,Lee, Bo-Han,Liao, Ping-Kuei,Fang, Ching-Shiang,Liu
-
experimental part
p. 480 - 484
(2012/07/30)
-
- Direct N-arylation of azaheterocycles with aryl halides under ligand-free condition
-
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
- Yang, Qichao,Wang, Yufang,Zhang, Baoji,Zhang, Mingjie
-
p. 2389 - 2393,5
(2020/09/16)
-
- Cu(OAc)2·H2O-catalyzed N-arylation of nitrogen-containing heterocycles
-
In the absence of any additional ligands, the efficient N-arylation of nitrogen-containing heterocycles with aryl iodides catalyzed by relative low catalyst amount of Cu(OAc)2·H2O was developed. This simple catalytic system is involved in the C-N cross-coupling reaction and works for a variety of pyrazole, pyrrole, imidazole, triazole, indole, benzoimidazole, benzotriazole, carbazole, and anilines as well as aryl iodides with different electronic properties. Highly efficient copper(II)-catalyzed N-arylation protocol was established.
- Xu, Zhong-Lin,Li, Hong-Xi,Ren, Zhi-Gang,Du, Wei-Yuan,Xu, Wei-Chang,Lang, Jian-Ping
-
supporting information; experimental part
p. 5282 - 5288
(2011/08/04)
-
- Complete assignment of NMR data of 22 phenyl-1H-pyrazoles' derivatives
-
Complete assignment of 1H and 13C NMR chemical shifts and J(1H/1H and 1H/19F) coupling constants for 22 1-phenyl-1H-pyrazoles' derivates were performed using the concerted application of 1H 1D and 1H, 13C 2D gs-HSQC and gs-HMBC experiments. All 1-phenyl-1H-pyrazoles' derivatives were synthesized as described by Finar and co-workers. The formylated 1-phenyl-1H-pyrazoles' derivatives were performed under Duff's conditions. Copyright
- De Oliveira, Aline Lima,Alves De Oliveira, Carlos Henrique,Mairink, Laura Maia,Pazini, Francine,Menegatti, Ricardo,Liao, Luciano Morais
-
scheme or table
p. 537 - 542
(2011/10/09)
-
- Transition-metal-free O-,S -, and N-arylation of alcohols, thiols, amides, amines, and related heterocycles
-
A new protocol for the Ullmann-type arylation process of different aromatic heterocycles without any transition-metal catalyst, implying the use of a combination of an excess of potassium hydroxide and dimethyl sulfoxide, is described. The reaction can be performed between a broad range of starting nucleophiles including phenol, alcohols, amines, nitrogen-containing five-membered systems such as pyrazoles, imidazoles, and indoles, and amides with haloarenes, iodide and bromide derivatives giving the best results, the possible pathway involving the in situ generation of the corresponding benzyne intermediate. When the reaction was performed with 2-iodoaniline and either carboxamides or isothiocyanato derivatives, the corresponding benzoazole derivatives were obtained.
- Cano, Rafael,Ramon, Diego J.,Yus, Miguel
-
experimental part
p. 654 - 660
(2011/03/20)
-
- Efficient iron/copper cocatalyzed N-arylation of arylamines with bromoarenes
-
Fe(acac)3 and Cu(OAc)2H2O were found to effectively promote the C-N cross-coupling reaction in the presence of K 2CO3 as the base. A series of diaryl amine with different substituents can be synthesized in moderate to good yields. This efficient and economic method is attractive for applications on an industrial scale. Georg Thieme Verlag Stuttgart - New York.
- Liu, Xiaoyan,Zhang, Songlin
-
supporting information; experimental part
p. 1137 - 1142
(2011/07/09)
-
- Ligands for copper-catalyzed C-N bond forming reactions with 1 Mol% CuBr as catalyst
-
Several new ligands were designed to promote copper-catalyzed Ullman C-N coupling reactions. In this group, 8-hydroxyquinolin-N-oxide was found to serve as a superior ligand for CuBr-catalyzed coupling reactions of aryl iodides, bromides, and chlorides with aliphatic amines and N-heterocycles under a low catalyst loading (1% [Cu] mol). Reactions with the inexpensive catalytic system display a high functional group tolerance as well as excellent chemoselectivity.
- Yang, Kai,Qiu, Yatao,Li, Zheng,Wang, Zhaoyang,Jiang, Sheng
-
experimental part
p. 3151 - 3159
(2011/06/23)
-
- A new, efficient and recyclable lanthanum(III) oxide-catalyzed C-N cross-coupling
-
A new and efficient protocol for the C-N cross-coupling of aryl halides with heteroaromatic amines in the presence of lanthanum(III) oxide (10 mol%) as a recyclable catalyst, N,N′-dimethylethylenediamine (DMEDA) (20 mol%) and potassium hydroxide (KOH) as a base in dimethyl sulfoxide (DMSO) at 110 °C has been developed. This inexpensive catalytic system is highly effective towards the amination of aryl halides with various nitrogen nucleophiles and is significantly tolerant towards other functional groups in the substrates. Copyright
- Murthy, S. Narayana,Madhav,Reddy, V. Prakash,Nageswar
-
supporting information; experimental part
p. 3241 - 3245
(2011/02/23)
-
- An effective N-ligand for copper-catalyzed N-arylation of triazole
-
An effective N-ligand for copper-catalyzed N-arylation of 1H-1,2,4- triazole has been developed. In the presence of Cu2O, Cs 2CO3, N-ligand-B, 1H-1,2,4-triazole were coupled with toluene to afford the corresponding product
- Yang, Yan,Jin, Yong-Sheng,Hu, Hong-Gang,Zhao, Qing-Jie,Zou, An,Wu, Qiu-Ye
-
experimental part
p. 7435 - 7437
(2012/07/28)
-
- Tripodal N-heterocyclic carbene complexes of palladium and copper: Syntheses, characterization, and catalytic activity
-
The tris-palladium tripodal N-heterocyclic carbene (NHC) complexes (timtebtBu){Pd(ICy)I2}3 (4a), (timteb tBu){Pd(PPh3)I2}3 (5a), and (timtebdipp){Pd(PPh3)I2}3 (5b) (timtebtBu = 1,3,5-{tris(tert-butylimidazol-2-ylidene)methyl}-2,4,6- triethylbenzene, 3a; ICy = 1,3-dicyclohexylimidazol-2-ylidene; timteb dipp = 1,3,5-{tris({2,6-diisopropylphenyl}imidazol-2-ylidene)methyl}- 2,4,6-triethylbenzene, 3b) were prepared by reaction of Pd(II) precursors with either the free carbenes or imidazolium salts. Treatment of [Cu(NCMe) 4]X (X = PF6, BF4) with 3a or 3b produced the tris-copper(I) bridged complexes [(timtebR) Cu3(μ3-O)]X (R = tBu, X = PF6, 6a; R = dipp, X = BF4, 6b). Complexes 4a, 5a, and 6a were structurally characterized. The palladium complexes were tested as catalysts for Suzuki-Miyaura and Sonogashira coupling reactions and the copper species also employed for the Sonogashira reaction, as well as for the Ullmann-type arylation of imidazoles and phenols.
- Ellul, Charles E.,Reed, Graham,Mahon, Mary F.,Pascu, Sofia I.,Whittlesey, Michael K.
-
experimental part
p. 4097 - 4104
(2011/01/03)
-
- METHOD FOR THE PREPARATION OF PHOSPHINE BUTADIENE LIGANDS, COMPLEXES THEREOF WITH COPPER AND USE THEREOF IN CATALYSIS
-
The present invention relates to a method for preparing phosphine butadiene-type ligands, and their use, particularly as catalytic metal ligands used in the reactions leading to the formation of carbon-carbon and carbon-heteroatom bonds.
- -
-
Page/Page column 19; 20
(2010/06/11)
-
- An efficient N-arylation of heterocycles with aryl-, heteroaryl-, and vinylboronic acids catalyzed by copper fluorapatite
-
N-Arylation of N-containing heterocycles, such as pyrazoles, imidazoles, and benzimidazoles with aryl-, heteroaryl-, and vinylboronic acids was efficiently carried out by copper fluorapatite (CuFAP) catalyst in MeOH at room temperature under base-free conditions. The N-arylated heterocycles were isolated in good-to-excellent yields.
- Kantam, Mannepalli Lakshmi,Venkanna, Gopaladasu Tirupati,Kumar, Kota Balaji Shiva,Subrahmanyam, Vura Bala
-
experimental part
p. 974 - 979
(2010/08/06)
-
- Iron complex-catalyzed N-arylation of pyrazoles under aqueous medium
-
Commercially available FeCl3·6H2O with conformationally rigid diamine ligand is a highly effective catalyst for N-arylation of pyrazoles using aryl and heteroaryl iodides. It is notable to show that this complex is tolerable under aqueous medium and particularly the whole reaction utilizes water as the sole solvent without any additional organic co-solvents and surfactants. Attempted study using other nitrogen nucleophiles is described. This newly developed system provides an alternative protocol to Cu- and Pd-catalyzed N-arylation reactions.
- Lee, Hang Wai,Chan, Albert S.C.,Kwong, Fuk Yee
-
experimental part
p. 5868 - 5871
(2010/01/11)
-
- Recyclable heterogeneous iron catalyst for C-N cross-coupling under ligand-free conditions
-
(Chemical Equation Presented) An efficient and ligand-free C-N cross-coupling of aryl halides with various heterocycles using Fe/Cg as a recyclable catalyst is reported. The yields are excellent to moderate. 2009 American Chemical Society.
- Swapna,Vijay Kumar,Prakash Reddy,Rama Rao
-
supporting information; experimental part
p. 7514 - 7517
(2009/12/28)
-
- Trinuclear copper(I) complexes with triscarbene ligands: Catalysis of C-N and C-C coupling reactions
-
Novel synthetic routes for the preparation of trinuclear copper(I) complexes with triscarbene ligands are presented, which yield higher purity products than the one previously described. The first crystal structure of one of these complexes is reported an
- Biffis, Andrea,Tubaro, Cristina,Scattolin, Elena,Basato, Marino,Papini, Grazia,Santini, Carlo,Alvarez, Eleuterio,Conejero, Salvador
-
experimental part
p. 7223 - 7229
(2010/02/15)
-