- Methanol as the C1source: Redox coupling of nitrobenzenes and alcohols for the synthesis of benzimidazoles
-
We present an operationally simple redox coupling for the synthesis of N-1 substituted benzimidazoles using feedstock building block 2-nitroaniline derivatives as the precursors and methanol as the C1 source. Higher atom, step, and redox economies and exc
- An, Jie,Lai, Zemin,Li, Hengzhao,Peng, Mengqi,Sun, Yanhao,Yan, Zihan,Yang, Ruoyan,Zhang, Yuntong
-
supporting information
p. 748 - 753
(2022/02/02)
-
- Functionalization of superparamagnetic Fe3O4@SiO2 nanoparticles with a Cu(II) binuclear Schiff base complex as an efficient and reusable nanomagnetic catalyst for N-arylation of α-amino acids and nitrogen-containing heterocycles with aryl halides
-
Fe3O4@SiO2 nanoparticles was functionalized with a binuclear Schiff base Cu(II)-complex (Fe3O4@SiO2/Schiff base-Cu(II) NPs) and used as an effective magnetic hetereogeneous nanocatalyst for the N-arylation of α-amino acids and nitrogen-containig heterocycles. The catalyst, Fe3O4@SiO2/Schiff base-Cu(II) NPs, was characterized by Fourier transform infrared (FTIR) and ultraviolet-visible (UV-vis) analyses step by step. Size, morphology, and size distribution of the nanocatalyst were studied by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and dynamic light scatterings (DLS) analyses, respectively. The structure of Fe3O4 nanoparticles was checked by X-ray diffraction (XRD) technique. Furthermore, the magnetic properties of the nanocatalyst were investigated by vibrating sample magnetometer (VSM) analysis. Loading content as well as leaching amounts of copper supported by the catalyst was measured by inductive coupled plasma (ICP) analysis. Also, thermal studies of the nanocatalyst was studied by thermal gravimetric analysis (TGA) instrument. X-ray photoelectron spectroscopy (XPS) analysis of the catalyst revealed that the copper sites are in +2 oxidation state. The Fe3O4@SiO2/Schiff base-Cu(II) complex was found to be an effective catalyst for C–N cross-coupling reactions, which high to excellent yields were achieved for α-amino acids as well as N-hetereocyclic compounds. Easy recoverability of the catalyst by an external magnet, reusability up to eight runs without significant loss of activity, and its well stability during the reaction are among the other highlights of this catalyst.
- Sardarian,Kazemnejadi,Esmaeilpour
-
-
- Synthesis, crystal structure, and catalytic activity of bridged-bis(N-heterocyclic carbene) palladium(II) complexes in selective Mizoroki-Heck cross-coupling reactions
-
A series of three 1,3-propanediyl bridged bis(N-heterocyclic carbene)palladium(II) complexes (Pd-BNH1, Pd-BNH2, and Pd-BNH3), with + I effect order of the N-substituents of the ligand (isopropyl > benzyl > methoxyphenyl), was the subject of a spectroscopic, structural, computational and catalytic investigation. The bis(NHC)PdBr2 complexes were evaluated in Mizoroki-Heck coupling reactions of aryl bromides with styrene or acrylate derivatives and showed high catalytic efficiency to produce diarylethenes and cinnamic acid derivatives. The X-ray structure of the most active palladium complex Pd-BNH3 shows that the Pd(II) center is bonded to the two carbon atoms of the bis(N-heterocyclic carbene) and two bromide ligands in cis position, resulting in a distorted square planar geometry. The NMR data of Pd-BNH3 are consistent with a single chair-boat rigid conformer in solution with no dynamic behavior of the 8-membered ring palladacycle in the temperature range 25–120 °C. The catalytic activities of three Pd-bridged bis(NHC) complexes in the Mizoroki-Heck cross-coupling reactions were not found to have a direct correlation with +I effect order of the N-substituents of the ligand. However, a direct correlation was found between the DFT calculated absolute softness of the three complexes with their respective catalytic activity. The highest calculated softness, in the case of Pd-BNH3, is expected to favor the coordination steps of both the soft aryl bromides and alkenes in the Heck catalytic cycle.
- El Ali, Bassam,Fettouhi, Mohammed,Iali, Wissam,Mansour, Waseem,Suleiman, Rami
-
-
- Ni-Catalyzed Dual C-H Annulation of Benzimidazoles with Alkynes for Synthesis of π-Extended Heteroarenes
-
Transition metal catalyzed dual C-H activation and annulation with alkynes was an attractive protocol to construct polycyclic π-extended structures. However, most of them were dominated by noble metal catalysts. Disclosed herein was the study of base-metal Ni-catalysis for dual C-H annulation of N-aromatic imidazole, which produced a range of desired polycyclic aza-quinolines in 48-95% yields. The use of bifunctional phosphine oxide ligand proved to be critical for success.
- Qi, Shao-Long,Li, Yue,Li, Jiang-Fei,Zhang, Tao,Luan, Yu-Xin,Ye, Mengchun
-
supporting information
p. 4034 - 4039
(2021/05/26)
-
- Efficient NIR electrochemiluminescent dyes based on ruthenium(ii) complexes containing an N-heterocyclic carbene ligand
-
Three new ruthenium(ii) complexes containing an N-heterocyclic carbene (NHC) ligand (RuNHC) have been successfully synthesized and proved to be efficient near-infrared (NIR) ECL (electrogenerated chemiluminescence) luminophores. In addition to the advanta
- Zhou, Yu-Yang,Ding, Yang-Ming,Zhao, Wei,Dong, Jian-Hua,Li, Liang-Zhi,Chen, Hong-Yuan,Xu, Jing-Juan
-
supporting information
p. 1254 - 1257
(2021/02/09)
-
- Cu(I)–N-heterocyclic carbene-catalyzed base free C–N bond formation of arylboronic acids with amines and azoles
-
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
-
-
- Cu(OAc)2-porphyrins as an efficient catalytic system for base-free, nature mimicking Chan–Lam coupling in water
-
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.
- Venkateswarlu, Katta,Rao, Kanusu Umamaheswara
-
-
- N -Arylation of (hetero)arylamines using aryl sulfamates and carbamates via C-O bond activation enabled by a reusable and durable nickel(0) catalyst
-
An effective and general aryl amination protocol has been developed using a magnetically recoverable Ni(0) based nanocatalyst. This new stable catalyst was prepared on Fe3O4@SiO2 modified by EDTA and investigated by FT-IR, EDX, TEM, XRD, DLS, FE-SEM, XPS, NMR, TGA, VSM, ICP and elemental analysis techniques. The reaction proceeded via carbon-oxygen bond cleavage of (hetero)aryl carbamates and sulfamates under simple and mild conditions without the use of any external ligands. This method demonstrated functional group tolerance in the N-arylation of various nitrogen-containing compounds as well as aliphatic amines, anilines, pyrroles, pyrazoles, imidazoles, indoles, and indazoles with good to excellent yields. Furthermore, the catalyst could be easily recovered by using an external magnetic field and directly reused at least six times without notable reduction in its activity. This journal is
- Dindarloo Inaloo, Iman,Majnooni, Sahar,Eslahi, Hassan,Esmaeilpour, Mohsen
-
p. 13266 - 13278
(2020/10/07)
-
- A Chemoselective and Desulfurative Chan–Lam Coupling: C–N Bond Formation between Benzimidazoline-2-Thiones and Arylboronic Acids
-
An efficient method for the chemoselective and desulfurative Chan–Lam cross-coupling based on benzimidazoline-2-thiones was developed. By modulating the amount of the catalyst Cu(OAc)2·H2O, alkali, temperature, and solvent, the desulfurizational C–N bond formation product (N-arylbenzimidazoles) could be selectively furnished smoothly. The features of this protocol are an inexpensive and readily available catalyst, ligand-free conditions, wide substrate scope, easy performance, and moderate to excellent yields. It shows potential synthetic value for the preparation of a diversity of arylbenzoheterocyclic compounds, which are potentially active in pharmaceuticals and agrochemicals.
- Chen, Jin-Quan,Liu, Xing,Guo, Jia,Dong, Zhi-Bing
-
supporting information
p. 2414 - 2424
(2020/03/23)
-
- Cu(i) based catalysts derived from bidentate ligands and studies on the effect of substituents for: N -arylation of benzimidazoles and indoles
-
A family of Cu(i) complexes [Cu(L1-4)(Cl)(PPh3)] (C1-C4) were synthesized from bidentate ligands L1-L4 (where L1 = (E)-2-(2-benzylidene-1-phenylhydrazinyl)pyridine, L2 = (E)-N,N-dimethyl-4-((2-phenyl-2-(pyridin-2-yl)hydrazono)methyl)aniline, L3 = (E)-2-(2
- Kumari, Sheela,Ratnam, Anand,Mawai, Kiran,Chaudhary, Virendra Kumar,Mohanty, Aurobinda,Ghosh, Kaushik
-
p. 19591 - 19597
(2020/12/05)
-
- Facile synthesis of hydrochar supported copper nanocatalyst for Ullmann C–N coupling reaction in water
-
The exploration of inexpensive and stable heterogeneous catalysts and application of green solvents for Ullmann C–N coupling reaction remain challenging. We present a facile fabrication of copper nanoparticles on hydrochar as prepared from natural, inexpensive and renewable chitosan together with in-situ reduction of copper salt in a one-pot hydrothermal carbonization process. The copper nanoparticles were uniformly dispersed on hydrochar by choosing block copolymer F127 as surfactant. Moreover, maleic acid was introduced to improve the hydrophilicity of hydrochar. The most active copper nanocomposite catalyst, that is, Cu/HCS-MA-F127, exhibited excellent catalytic activity for Ullmann C–N coupling reaction in water. The nature of the Cu/HCS-MA-F127 was characterized by FTIR spectroscopy, TG, XRD, SEM and XPS. Moderate to excellent yields of aimed products were gained by using this catalytic strategy. Moreover, the Cu/HCS-MA-F127 catalyst can be reused by simple centrifugal recovery with a stable performance.
- Ge, Xin,Ge, Meng,Chen, Xinzhi,Qian, Chao,Liu, Xuemin,Zhou, Shaodong
-
-
- Highly-efficient N-arylation of imidazole catalyzed by Cu(II) complexes with quaternary ammonium-functionalized 2-acetylpyridine acylhydrazone
-
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
- 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
-
-
- Ligand complex of copper (II) supported on superparamagnetic Fe3O4?SiO2 nanoparticles: an efficient and magnetically separable catalyst for N-arylation of nitrogen-containing heterocycles with aryl halides
-
In this study, we introduce the ligand complex of copper (II) supported on superparamagnetic Fe3O4?SiO2 nanoparticles as a highly intriguing magnetic catalyst in N-arylation of nitrogen heterocycles with aryl halides. The present methodology offers several advantages such as; low catalyst loading, the use of magnetically recoverable and reusable catalyst, high to excellent yields without using any external ligands or additives, short reaction times and simplicity of operation. Also, the magnetic catalyst could be easily separated from the final product by an external magnet and reused up to seven times without any significant loss of activity. Therefore, this separation strategy with negligible leaching makes Fe3O4?SiO2/ligand/Cu(II) an economical catalyst to perform this transformation.
- Zahmatkesh, Saeed,Esmaeilpour, Mohsen,Mollaiy Poli, Azade
-
p. 323 - 334
(2019/11/05)
-
- A designed bi-functional sugar-based surfactant: Micellar catalysis for C-X coupling reaction in water
-
A bi-functional sugar-based surfactant ALA14 was designed as the ligand and micelle constructor and demonstrated to promote the copper-catalyzed C-X coupling reaction in water. The nature of this micelle, formed by sugar-based surfactants, was investigated with CMC, DLS, and TEM, by which encapsulation and aggregation of the substrates in micelles were verified. Additionally, it was addressed by 1H-NMR analysis that the enrichment position of the substrates is in the lipophilic alkyl chain. Finally, moderate to excellent yields of the aimed products were obtained in this work. This remarkably simple strategy expanded the scope of C-X coupling reaction in water; most notably, both water and ALA14 can be recycled and reused.
- Ge, Xin,Zhang, Shihui,Chen, Xinzhi,Liu, Xuemin,Qian, Chao
-
supporting information
p. 2771 - 2776
(2019/06/13)
-
- A Newly Designed Carbohydrate-Derived Alkylamine Promotes Ullmann Type C-N Coupling Catalyzed by Copper in Water
-
A green and biodegradable carbohydrate-derived alkylamine was designed and employed as ligand for Ullmann type C-N coupling catalyzed by copper in water. The coupling of aryl iodide and N-nucleophiles were examined and moderate to excellent yields were obtained. In addition, the in-water coupling strategy was expanded successfully to the reaction of indoles with 4-iodoanisole. By measuring the solubility, it is speculated that carbohydrate-derived alkylamine plays the role of chelating copper and promoting the dissolution of 4-iodoanisole in water. Remarkably, this methodology was environmentally friendly and economical because of the use of aqueous media in place of organic solvents.
- Zhou, Guoquan,Chen, Wen,Zhang, Shihui,Liu, Xuemin,Yang, Zehui,Ge, Xin,Fan, Hua-Jun
-
supporting information
p. 193 - 198
(2019/01/14)
-
- Preparation method of diarylamine compound
-
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.
- -
-
Paragraph 0070; 0071; 0072
(2019/04/26)
-
- Efficient N-arylation of azole compounds utilizing selective aryl-transfer TMP-iodonium(III) reagents
-
It was determined that diaryliodonium(III) triflates bearing a trimethoxybenzene (TMP) auxiliary are more reactive than the reported selective aryl-transfer iodonium salts in the N-arylation of benzimidazoles and other types of azole compounds under catalytic conditions. The TMP-iodonium(III) salts can thus effectively facilitate the reaction at 50 °C or below, producing the corresponding N-arylated biaryls without the formation of TMP-derived coupling byproducts. Utilization of this TMP reagent under mild conditions would prevent the underlying problem of participation of the auxiliary group in the coupling reactions, which is observed while using the iodonium(III) salts that require elevated temperatures.
- Koseki, Daichi,Aoto, Erika,Shoji, Toshitaka,Watanabe, Kazuma,In, Yasuko,Kita, Yasuyuki,Dohi, Toshifumi
-
supporting information
p. 1281 - 1286
(2019/04/10)
-
- Regioselective Ortho Amination of an Aromatic C-H Bond by Trifluoroacetic Acid via Electrochemistry
-
A trifluoroacetic acid-facilitated ortho amination of alkoxyl arene has been established via anodic oxidation in an undivided cell. In the absence of any additional metal or oxidant reagents, a series of aromatic and heteroaromatic amine derivatives have
- Wang, Jing-Hao,Lei, Tao,Nan, Xiao-Lei,Wu, Hao-Lin,Li, Xu-Bing,Chen, Bin,Tung, Chen-Ho,Wu, Li-Zhu
-
supporting information
p. 5581 - 5585
(2019/08/01)
-
- An efficient class of bis-NHC salts: Applications in Pd-catalyzed reactions under mild reaction conditions
-
This study describes an efficient class of bis-N-heterocyclic carbene (bis-NHC) salts that can be easily made from commercially available and inexpensive starting materials. The application of these salts to Pd-catalyzed reactions is described. The palladium (Pd) catalyst generated in situ was highly effective under mild reaction conditions.
- Chiu, Chien-Cheng,Chiu, Hui-Tzu,Lee, Dong-Sheng,Lu, Ta-Jung
-
p. 26407 - 26415
(2018/08/04)
-
- 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
-
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.
- Esmaeilpour, Mohsen,Sardarian, Ali Reza,Firouzabadi, Habib
-
-
- Efficient Ullmann C-X coupling reaction catalyzed by a recoverable functionalized-chitosan supported copper complex
-
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.
- Liu, Xuemin,Chang, Shuo,Chen, Xinzhi,Ge, Xin,Qian, Chao
-
supporting information
p. 16013 - 16020
(2018/10/04)
-
- Chan-Lam cross-coupling reaction based on the Cu2S/TMEDA system
-
A catalyst based on the readily available Cu2S/TMEDA system using a stable copper(I) source was developed for the Chan-Lam cross-coupling reaction. The capability of the catalyst was demonstrated with 1H-benzo[d]imidazol-2(3H)-one, 1H-benzo[d]imidazole, and 1H-imidazole together with electron-deficient, electron-rich, and sterically demanding boronic acids at room temperature in the presence of atmospheric oxygen to give the cross-coupling products in moderate to excellent yields. In addition, the coupling reaction of 1H-benzo[d]imidazole with several pinacol or neopentylglycol boronates indicated further potential of the catalyst. The reaction conditions tolerate the hydroxyl and bromo functional groups. The catalytic system also enables to synthesize the mono-N-substituted anilines from primary aliphatic amines. However, the two model compounds for the secondary and aromatic amines, piperidine and aniline, do not react. Two sterically demanding products with the restricted C–N bond rotation, synthesized by the N-arylation of 1H-benzo[d]imidazol-2(3H)-one with o-tolylboronic acid, enabled to confirm the atropisomers prepared by the Chan-Lam cross-coupling reaction. Furthermore, an example of one-pot Chan-Lam and Suzuki-Miyaura reaction has been reported.
- Janíková, Kate?ina,Jedinák, Luká?,Volná, Tereza,Canka?, Petr
-
p. 606 - 617
(2018/01/01)
-
- N, O-Bidentate ligand-tunable copper(II) complexes as a catalyst for Chan-Lam coupling reactions of arylboronic acids with 1 H-imidazole derivatives
-
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
-
p. 8984 - 8988
(2018/12/10)
-
- CopperII phthalocyanine as an efficient and reusable catalyst for the N-arylation of nitrogen containing heterocycles
-
Copper phthalocyanine (CuIIPc) was found to be an efficient catalyst for the catalyzed N-arylation of N–H heterocycles with aryl iodides and bromides under mild reaction conditions. A variety of hindered and functionalized N–H heterocycles and aryl halides were successfully used as the substrates for the given catalytic reaction and were transformed in good to excellent yields.
- Yadav, Kumar Karitkey,Narang, Uma,Bhattacharya, Soumee,Chauhan, Shive M.S.
-
supporting information
p. 3044 - 3048
(2017/07/17)
-
- Immobilized Pd nanoparticles on silica-starch substrate (PNP-SSS): Efficient heterogeneous catalyst in Buchwald–Hartwig C–N cross coupling reaction
-
An immobilized Pd nanoparticle on silica-starch substrate (PNP-SSS) is introduced as an efficient heterogeneous catalyst in Pd-catalyzed Buchwald–Hartwig C–N cross coupling reaction. A range of aryl amines were synthesized using reaction of aryl halides (chloride, bromide and iodide) and amines using PNP-SSS catalyst in good to excellent yields. The PNP-SSS catalyst shows high catalytic activity in C-N bond formation reaction and it is reusable in this reaction at least for five times without significant decreasing in its catalytic activity.
- Panahi, Farhad,Daneshgar, Fatemeh,Haghighi, Fatemeh,Khalafi-Nezhad, Ali
-
p. 210 - 217
(2017/10/09)
-
- Magnetically recoverable copper nanorods and their catalytic activity in Ullmann cross-coupling reaction
-
A novel polydentate ligand supported on Fe3O4@SiO2 was designed and demonstrated for the synthesis of Cu nanorods. The Fe3O4@SiO2/EP.EN.EG@Cu was characterized using X-ray diffraction, ther
- Rajabzadeh, Maryam,Eshghi, Hossein,Khalifeh, Reza,Bakavoli, Mehdi
-
-
- Carbothioamide as Highly Efficient Ligand for Copper-catalyzed Room Temperature Chan–Lam Cross-Coupling Reaction
-
The catalytic activity of three N,S-donor ligands, viz L1 [2-(4-methoxybenzylidene)-N-phenylhydrazinecarbothioamide], L2 [2,2′-(1,2-diphenylethane-1,2-diylidene)bis(hydrazinecarbothioamide)] and L3 [2-(4-methoxybenzylidene)hydrazinecarbothioamide] has been reported for N-arylation of imidazoles with arylboronic acids in ethanol at room temperature. The method was found to be applicable in N-arylation for a wide range of electronically diverse arylboronic acids with imidazoles having modest to excellent isolated yields. The in situ generated copper(II) complex of the ligand namely, 2-(4-methoxybenzylidene)-N-phenylhydrazinecarbothioamide (L1) was found to be highly efficient homogeneous catalyst for N-arylation reaction.
- Baruah, Jayantajit,Gogoi, Kongkona,Dewan, Anindita,Borah, Geetika,Bora, Utpal
-
p. 1203 - 1208
(2017/10/25)
-
- Base-assisted, copper-catalyzed N-arylation of (benz)imidazoles and amines with diarylborinic acids
-
N-Arylation of (benz)imidazoles and amines with diarylborinic acids as cost-effective aryl source has been efficiently effected via Cu(OAc)2-catalyzed Chan-Lam coupling in assistance of tetramethylethylenediamine (TMEDA) in methanol and pyridine (Py) in dichloromethane, respectively, in air at room temperature. The diarylborinic acids could be well accommodated by the Chan-Lam coupling oxidative conditions containing a proper combination of bases and solvents. The steric hindrance appeared to affect the copper-catalyzed N-arylation using the high-order arylboron reagent more significantly than the electronic factors, especially for low reactive anilines and aliphatic amines.
- Guan, Changwei,Feng, Yuanyuan,Zou, Gang,Tang, Jie
-
p. 6906 - 6913
(2017/11/03)
-
- SMALL MOLECULE INHIBITORS OF DYRK1A AND USES THEREOF
-
This invention is in the field of medicinal chemistry. In particular, the invention relates to a new class of small-molecules having a benzimidazole or imidazopyridine structure which function as inhibitors of DYRK1A protein, and their use as therapeutics for the treatment of Alzheimer's disease, Down syndrome, glioblastoma, autoimmune diseases, inflammatory disorders (e.g., airway inflammation), and other diseases.
- -
-
-
- N-Arylation of nitrogen containing heterocycles with aryl halides using copper nanoparticle catalytic system
-
Cu nanoparticles promoted N-arylation of NH-heterocycles with aryl halides is an effective and inexpensive method. In this synthetic protocol, good to excellent yields are obtained. Both aryl iodide and aryl bromide are compatible with the reaction conditions.
- Pai, Gita,Chattopadhyay, Asoke P.
-
p. 3140 - 3145
(2016/07/06)
-
- 1,4-Dihydroxyanthraquinone-copper(II) supported on superparamagnetic Fe3O4@SiO2: An efficient catalyst for N -arylation of nitrogen heterocycles and alkylamines with aryl halides and click synthesis of 1-aryl-1,2,3-triazole derivatives
-
1,4-Dihydroxyanthraquinone-copper(ii) supported on a superparamagnetic Fe3O4@SiO2 catalyst was employed for the N-arylation of nitrogen heterocycles and alkylamines with aryl halides to afford the corresponding coupled products in good to excellent yields without using external ligands or additives as promoters. Also, we have reported this recyclable catalytic system for efficient synthesis of 1-aryl-1,2,3-triazole derivatives in excellent yields. The desired triazoles were obtained from the reaction of the corresponding aryl boronic acid derivatives, alkyne, NaN3, and 0.5 mol% catalyst in water/acetonitrile as the solvent at room temperature without the additional use of an external reducing agent. These methods show notable advantages such as the heterogeneous nature of the catalyst, low catalyst loading, easy preparation, excellent yields, short reaction times and simplicity of operation. Also, the catalyst can be separated from the reaction mixture by applying a permanent magnet externally and can be reused in six consecutive reaction cycles without significant loss of activity.
- Zahmatkesh, Saeed,Esmaeilpour, Mohsen,Javidi, Jaber
-
p. 90154 - 90164
(2016/10/09)
-
- 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)
-
- Immobilized Pd(0) nanoparticles on phosphine-functionalized graphene as a highly active catalyst for Heck, Suzuki and N-arylation reactions
-
In this study, a phosphine group was chemically grafted to the surface of graphene in order to prepare a reusable ligand with high surface area, incorporating a phosphine moiety. The treatment of graphene oxide (GO) with hydroxide followed by an aqueous work-up yields an OH-functionalized graphene material (GOH) via ring-opening of the epoxide groups. Reaction of GOH with chlorodiphenylphosphine (ClPPh2) gives a new material, GOPPh2 (PFG), which can be used for stabilization of metal nanoparticles or complexation of transition metals in order to prepare a reusable metal catalyst. Stabilization of palladium nanoparticles on the surface of GOPPh2 resulted in the production of an efficient heterogeneous Pd catalyst (PFG-Pd) for application in C-C and C-N bond formation reactions. The PFG-Pd catalyst was characterized using some different microscopic and spectroscopic techniques such as FT-IR, XRD, TEM, SEM, EDX, and ICP analysis. The applicability of the PFG-Pd catalyst was evaluated in Heck, Suzuki and N-arylation reactions. The catalyst system showed high catalyst activity in these processes and the target products were obtained in high isolated yields. The PFG-Pd catalyst was reusable in these reactions for at least 5 times with no significant decrease in its catalytic activity.
- Fareghi-Alamdari, Reza,Haqiqi, Mohsen G.,Zekri, Negar
-
p. 1287 - 1296
(2016/02/19)
-
- Combined experimental/theoretical study of D-glucosamine promoted Ullmann-type C-N coupling catalyzed by copper(I): Does amino really count?
-
Ullmann type C-N coupling reaction catalyzed by copper(I) with D-glucosamine derivatives as promoters was studied by means of combined experimental/theoretical investigation. The catalytic role of D-glucosamine was addressed. In contrast with previous speculations, the amino group may not count in the catalytic cycle in which the oxidative addition/reductive elimination mechanism works. Experimental results are in good agreement with theoretical findings. Extensive work indicates the wide applicability of the C-N coupling strategy exploited in this work.
- Ge, Xin,Chen, Xinzhi,Qian, Chao,Zhou, Shaodong
-
p. 29638 - 29645
(2018/06/04)
-
- Efficient Ullmann C-N coupling catalyzed by a recoverable oligose-supported copper complex
-
The natural compound β-cyclodextrin supported copper complex (CuIβ-CD) was prepared and employed as catalyst for an Ullmann-type C-N coupling reaction of N-nucleophiles and aryl halides under mild conditions. Reactions with different substrates were examined, and moderate to excellent yields were obtained. In addition to the high efficiency, the reaction system is also noticeable due to the excellent recoverability and reusability of the catalyst.
- Ge, Xin,Chen, Xinzhi,Qian, Chao,Zhou, Shaodong
-
p. 58898 - 58906
(2016/07/06)
-
- 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)
-
- A triazine-phosphite polymeric ligand bearing cage-like P,N-ligation sites: An efficient ligand in the nickel-catalyzed amination of aryl chlorides and phenols
-
A novel P,N-ligand was introduced for efficient Ni-catalyzed amination of aryl chlorides. Reaction of cyanuric acid (1,3,5-triazine-2,4,6-triol) and trichlorophosphine (PCl3) resulted in the production of a new porous material (TPPM) containing triazine rings with phosphite moieties in a sheet morphology. Cavities in the prepared compound create sites on the surface of the material with appropriate ligation character to coordinate with metals for catalytic purposes. The nickel-catalyzed amination of aryl chlorides and of phenols in their 2,4,6-triaryloxy-1,3,5-triazine (TAT) protected form were efficiently accomplished in the presence of this easily prepared and reusable P,N-ligand under mild reaction conditions. More importantly, TPPM was reusable for 5 iterations following this protocol without significantly decreasing in its activity.
- Panahi, Farhad,Roozbin, Fatemeh,Rahimi, Sajjad,Moayyed, Mohammadesmaeil,Valaei, Aria,Iranpoor, Nasser
-
supporting information
p. 80670 - 80678
(2016/10/12)
-
- Heterogeneous sequential N-arylation of N-heterocycles over copper anchored mesoporous silica catalyst
-
N-Arylation reaction of N-heterocyclic compounds has been carried out in excellent yield using copper anchored SBA-15 catalyst. Sequential N-arylation reactions employing single catalyst under heterogeneous condition provides a straightforward access to a
- Das, Soma,Maity, Tanmoy,Koner, Subratanath
-
-
- Copper(I) 3-methylsalicylate mediates the Chan-Lam N-arylation of heterocycles
-
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.
- Farahat, Abdelbasset A.,Boykin, David W.
-
supporting information
p. 245 - 252
(2015/10/29)
-
- Site-selective arene C-H amination via photoredox catalysis
-
Over the past several decades, organometallic cross-coupling chemistry has developed into one of the most reliable approaches to assemble complex aromatic compounds from preoxidized starting materials. More recently, transition metal-catalyzed carbon-hydrogen activation has circumvented the need for preoxidized starting materials, but this approach is limited by a lack of practical amination protocols. Here, we present a blueprint for aromatic carbon-hydrogen functionalization via photoredox catalysis and describe the utility of this strategy for arene amination. An organic photoredox-based catalyst system, consisting of an acridinium photooxidant and a nitroxyl radical, promotes site-selective amination of a variety of simple and complex aromatics with heteroaromatic azoles of interest in pharmaceutical research. We also describe the atom-economical use of ammonia to form anilines, without the need for prefunctionalization of the aromatic component.
- Romero, Nathan A.,Margrey, Kaila A.,Tay, Nicholas E.,Nicewicz, David A.
-
p. 1326 - 1330
(2015/10/12)
-
- Cu(0)@Al2O3/SiO2 NPs: An efficient reusable catalyst for the cross coupling reactions of aryl chlorides with amines and anilines
-
The C-N cross coupling reaction of aryl chlorides with various alkyl/aryl amines catalyzed by copper nanoparticles impregnated on alumina/silica support (Cu(0)@Al2O3/SiO2) was investigated. The prepared catalyst was characterized for its intrinsic physico-chemical and textural properties using XRD, XPS, HR-TEM, BET surface area, SEM-EDAX, H2-TPR and ICP-AES techniques. The catalyst exhibits excellent reactivity and efficacy in the cross-coupling of a wide range of alkyl/aryl amines including challenging anilines with aryl chlorides. The catalyst offers significant advantages such as brevity, milder reaction conditions, excellent yields and high functional group tolerance for C-N cross coupling when compared with the other reported methods. Moreover, this atom-economical methodology does not require an additional ligand or co-catalyst/activator. The Cu(0)@Al2O3/SiO2 catalyst was efficiently applied to a gram scale synthesis of 7-chloro-4-(4-(2-nitrophenyl)piperazin-1-yl)quinolone (2k). The robustness of the catalyst was examined by reusing it for five consecutive runs.
- Reddy, P. Linga,Arundhathi,Rawat, Diwan S.
-
p. 92121 - 92127
(2015/11/17)
-
- 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
-
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
-
p. 44105 - 44116
(2014/12/10)
-
- Open-air N-arylation of N-H heterocycles with arylboronic acids catalyzed by copper(II) Schiff base complexes
-
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.
- Islam,Dey, Ram Chandra,Roy, Anupam Singha,Paul, Sumantra,Mondal, Sanchita
-
p. 961 - 969
(2015/01/09)
-
- Unique copper-salen complex: An efficient catalyst for N-arylations of anilines and imidazoles at room temperature
-
We have reported here the catalytic activity of a unique Cu-salen type complex in N-arylation of anilines with arylboronic acids in water. The protocol is found to be applicable for a wide range of electronically diversified arylboronic acids and anilines with excellent yields of the isolated product. Further the scope of this protocol has been extended to the synthesis of various N-aryl imidazoles in iso-propanol.
- Gogoi, Ankur,Sarmah, Gayatri,Dewan, Anindita,Bora, Utpal
-
-
- Copper(I) 3-methylsalicylate, an efficient catalyst for N-arylation of heterocycles under moderate reaction conditions
-
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.
-
supporting information
p. 3049 - 3051
(2014/05/20)
-
- 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)
-
- Monodentate palladium complexes bearing abnormal and normal carbene ligands with a formally identical steric environment
-
We report a series of novel isomeric Pd(II) complexes with monodentate abnormal and normal carbene ligands, possessing a formally identical steric environment around the metal center. The corresponding ligand precursors were prepared via the key steps based on Pd-catalyzed direct C-H arylation between imidazo[1,2-a]pyridine and aryl bromides and Cu-catalyzed C-N coupling reactions between benzoimidazole and aryl bromides. The new complexes were characterized by 1D and 2D NMR spectroscopy, X-ray crystallography, and elemental analysis. The isomeric pairs of ligands show minor differences among their steric properties, which were examined by calculating their buried volume. The abnormal carbene Pd(II) complexes were found to be more efficient in catalyzing Mizoroki-Heck coupling, direct C-H arylation, and decarboxylative coupling reactions, which can be clearly attributed to a stronger electronic donating effect of the abnormal carbene ligands.
- Ke, Chun-Hung,Kuo, Bing-Chiuan,Nandi, Debkumar,Lee, Hon Man
-
p. 4775 - 4784
(2013/09/24)
-
- A versatile approach to ullmann C-N couplings at room temperature: New families of nucleophiles and electrophiles for photoinduced, copper-catalyzed processes
-
The use of light to facilitate copper-catalyzed cross-couplings of nitrogen nucleophiles can enable C-N bond formation to occur under unusually mild conditions. In this study, we substantially expand the scope of such processes, establishing that this approach is not limited to reactions of carbazoles with iodobenzene and alkyl halides. Specifically, we demonstrate for the first time that other nitrogen nucleophiles (e.g., common pharmacophores such as indoles, benzimidazoles, and imidazoles) as well as other electrophiles (e.g., hindered/deactivated/heterocyclic aryl iodides, an aryl bromide, an activated aryl chloride, alkenyl halides, and an alkynyl bromide) serve as suitable partners. Photoinduced C-N bond formation can be achieved at room temperature using a common procedure with an inexpensive catalyst (CuI) that does not require a ligand coadditive and is tolerant of moisture and a variety of functional groups.
- Ziegler, Daniel T.,Choi, Junwon,Munoz-Molina, Jose Maria,Bissember, Alex C.,Peters, Jonas C.,Fu, Gregory C.
-
supporting information
p. 13107 - 13112
(2013/09/24)
-
- CuI/8-hydroxyquinalidine promoted N-arylation of indole and azoles
-
An efficient catalytic system of CuI/8-hydroxyquinalidine was developed for the coupling of aryl iodides and indole as well as some azoles. The reaction could be carried out at 90°C under the condition of relatively low catalyst loading, affording various
- Zhang, Yihua,Yang, Xinye,Xing, Hui,Zhang, Ye,Lai, Yisheng,Jiang, Yongwen,Ma, Dawei
-
experimental part
p. 875 - 880
(2012/05/21)
-
- A reusable polymer supported copper catalyst for the C-N and C-O bond cross-coupling reaction of aryl halides as well as arylboronic acids
-
A simple and industrially viable protocol for C-N and C-O coupling was reported here. The polymer supported heterogeneous copper catalyst was prepared from chloromethyl polystyrene using a simple procedure. O-Arylation of substituted phenols with various aryl halides was achieved using this copper catalyst in DMSO medium. This heterogeneous copper catalyst, also efficiently works for the N-arylation of N-H heterocycles with aryboronic acids in methanol. This catalyst was also effective in amination reaction of primary amines with aryl halides as well as arylboronic acids in DMSO medium. The effects of solvent, base and temperature for the O-Arylation and amination reactions were reported. Further, the catalyst can be easily recovered quantitatively by simple filtration and reused up to several times without sufficient loss of its catalytic activity.
- Islam, Sk.Manirul,Mondal, Sanchita,Mondal, Paramita,Roy, Anupam Singha,Tuhina,Salam, Noor,Mobarak, Manir
-
experimental part
p. 4264 - 4274
(2012/01/06)
-