- Osmium(II)-bis(dihydrogen) complexes containing C aryl, C NHC-chelate ligands: Preparation, bonding situation, and acidity
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The hexahydride complex OsH6(PiPr3)2 (1) reacts with the BF4-salts of 1-phenyl-3-methyl-1-H-benzimidazolium, 1-phenyl-3-methyl-1-H-5,6-dimethyl-benzimidazolium, and 1-phenyl-3-methyl-1-H-imidazolium t
- Bolao, Tamara,Esteruelas, Miguel A.,Fernndez, Israel,Oate, Enrique,Palacios, Adrin,Tsai, Jui-Yi,Xia, Chuanjun
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- Synthesis of 1-substituted benzimidazole metal complexes and structural characterization of dichlorobis(1-phenyl- 1H-benzimidazole-kN 3)cobalt(II) and dichlorobis (1-phenyl-1H-benzimidazole-kN 3)zinc(II)
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The Co(II), Zn(II), Ni(II), Cu(II), and Fe(II) complexes of 1-phenylbenzimidazole were synthesized and characterized by NMR and elemental analyses. The crystal structures of dichlorobis(1-phenyl-1H-benzimidazole-N 3)cobalt(II) and dichlorobis(1-phenyl-1H-benzimidazole- kN 3)zinc(II) have been determined by single-crystal X-ray diffraction.
- Sireci, Nihat,Yilmaz, Uelkue,Kuecuekbay, Hasan,Akkurt, Mehmet,Baktir, Zeliha,Tuerktekin, Sevim,Bueykgngoer, Orhan
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- Heteroleptic platinum(ii) NHC complexes with a ?C? cyclometalated ligand-synthesis, structure and photophysics
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Platinum(ii) complexes [(NHC)Pt(L)] with various β-diketonate based auxiliary ligands (L: 3-meacac = 3-methylacetylacetonato, dpm = dipivaloylmethanato, dbm = dibenzoylmethanato, mesacac = dimesitoylmethanato, duratron = bis(2,3,5,6-tetramethylbenzoyl)methanato) and a ?C? cyclometalated N-heterocyclic carbene ligand (NHC: dpbic = 1,3-diphenylbenzo[d]imidazol-2-ylidene, dpnac = 1,3-diphenylnaphtho[2,3-d]imidazol-2-ylidene or bnbic = 1-phenyl-3-benzylbenzo[d]imidazol-2-ylidene) were found to show different aggregation and photophysical properties depending on the auxiliary ligand. Eight complexes were prepared from a silver(i)-NHC intermediate by transmetalation, cyclometalation and subsequent treatment with potassium-tert-butanolate and β-diketone. They were fully characterized by standard techniques including 195Pt NMR. Five complexes were additionally characterized by 2D NMR spectroscopy (COSY, HSQC, HMBC and NOESY). Solid-state structures of five complexes could be obtained and show the tendency of the square-planar compounds to form pairs with different Pt-Pt distances depending on the bulkiness of the substituents at the auxiliary ligand. The result of the photophysical measurements in amorphous PMMA films reveals quantum yields of up to 85% with an emission maximum in the blue region and comparatively short decay lifetimes (3.6 μs). Density functional theory (DFT/TD-DFT) calculations were performed to elucidate the emission process and revealed a predominant 3ILCT/3MLCT character. Organic light-emitting devices (OLEDs) comprising one of the complexes achieved 12.6% EQE, 11.9 lm W-1 luminous efficacy and 25.2 cd A-1 current efficiency with a blue emission maximum at 300 cd m-2. The influence of an additional hole-transporter in the emissive layer was investigated and found to improve the device lifetime by a factor of seven.
- Tronnier, Alexander,Heinemeyer, Ute,Metz, Stefan,Wagenblast, Gerhard,Muenster, Ingo,Strassner, Thomas
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- A PEG/copper(i) halide cluster as an eco-friendly catalytic system for C-N bond formation
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The catalytic activities of eight copper(i) halide clusters assembled from copper(i) halide and ferrocenyltelluroethers, 1-8, were investigated in C-N formation under various conditions. A catalytic procedure using poly(ethylene glycol) (PEG-400) as a gre
- Li, Cheng-An,Ji, Wei,Qu, Jian,Jing, Su,Gao, Fei,Zhu, Dun-Ru
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- Twist it! the acid-dependent isomerization of homoleptic carbenic iridium(III) complexes
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The first successful meridional to facial isomerization of homoleptic carbenic iridium(iii) complexes is presented. The Br?nsted-acid-mediated procedure allows the conversion of large amounts of material and additionally provides an in situ purification b
- Osiak, Jaroslaw G.,Setzer, Tobias,Jones, Peter G.,Lennartz, Christian,Dreuw, Andreas,Kowalsky, Wolfgang,Johannes, Hans-Hermann
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- Using Methanol as a Formaldehyde Surrogate for Sustainable Synthesis of N-Heterocycles via Manganese-Catalyzed Dehydrogenative Cyclization
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The development of an efficient and sustainable synthetic route for formaldehyde production from renewable feedstock, especially in combination with a subsequent transformation to straightforwardly construct valuable chemicals, is highly desirable. Herein, we report a novel manganese-catalyzed dehydrogenative cyclization of methanol as a formaldehyde surrogate with a variety of dinucleophiles for facile synthesis of N-heterocycles. The in situ generated formaldehyde via catalytic methanol dehydrogenation can be selectively trapped by diverse dinucleophiles to avoid several possible side reactions. The utility of this transformation is further highlighted by its successful application to the synthesis of 13C-labeled N-heterocycles using 13CH3OH as a readily accessible 13C-isotope reagent.
- Li, Yibiao,Liu, Qiang,Shao, Zhihui,Yuan, Shanshan
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supporting information
(2022/02/23)
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- Methanol as the C1source: Redox coupling of nitrobenzenes and alcohols for the synthesis of benzimidazoles
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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
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supporting information
p. 748 - 753
(2022/02/02)
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- 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
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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
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- Copper nanoparticle anchored biguanidine-modified Zr-UiO-66 MOFs: a competent heterogeneous and reusable nanocatalyst in Buchwald-Hartwig and Ullmann type coupling reactions
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We have designed a functionalized metal-organic framework (MOF) of UiO topology as a support, with an extremely high surface area, adjustable pore sizes and stable crystalline coordination polymeric structure and implanted copper (Cu) nanoparticles thereon. The core three dimensional Zr-derived MOF (UiO-66-NH2) was modified with a biguanidine moiety following a covalent post-functionalization approach. The morphological and physicochemical features of the material were determined using analytical methods such as FT-IR, SEM, TEM, EDX, atomic mapping, XRD and ICP-OES. The SEM and XRD results justified the unaffected morphology of Zr-MOF after structural modifications. The as-synthesized UiO-66-biguanidine/Cu nanocomposite was catalytically explored in the aryl and heteroaryl Buchwald-Hartwig C-N and Ullmann type C-O cross coupling reactions with excellent yields. A library of biaryl amine and biaryl ethers was synthesized over the catalyst under mild and green conditions. Furthermore, the catalyst was isolated by centrifugation and recycled 11 times with no significant copper leaching or change in its activity.
- Veisi, Hojat,Neyestani, Narges,Pirhayati, Mozhgan,Ahany Kamangar, Sheida,Lotfi, Shahram,Tamoradi, Taiebeh,Karmakar, Bikash
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p. 22278 - 22286
(2021/07/02)
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- L-Proline N-oxide dihydrazides as an efficient ligand for cross-coupling reactions of aryl iodides and bromides with amines and phenols
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A novel catalytic system based on L-proline N-oxide/CuI was developed and applied to the cross-coupling reactions of various N- and O- nucleophilic reagents with aryl iodides and bromides. This strategy featured in the employment of an-proline derived dihydrazides N-oxide compound as the superior supporting ligand. By using this protocol, a variety of products, including N-arylimidazoles, N-arylpyrazoles, N-arylpyrroles, N-arylamines, and aryl ethers, were synthesized with up to 99% yield.
- Ding, Zhiqiang,Nie, Nan,Chen, Tian,Meng, Lingxin,Wang, Gongshu,Chen, Zhangpei,Hu, Jianshe
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supporting information
(2020/12/21)
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- Ni-Catalyzed Dual C-H Annulation of Benzimidazoles with Alkynes for Synthesis of π-Extended Heteroarenes
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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
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supporting information
p. 4034 - 4039
(2021/05/26)
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- Efficient NIR electrochemiluminescent dyes based on ruthenium(ii) complexes containing an N-heterocyclic carbene ligand
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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
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supporting information
p. 1254 - 1257
(2021/02/09)
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- ORGANOMETALLIC COMPOUND AND ORGANIC LIGHT-EMITTING DEVICE INCLUDING THE SAME
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Provided are an organometallic compound represented by Formula 1 and an organic light-emitting device including the same. The organic light-emitting device includes: a first electrode, a second electrode, and an organic layer between the first electrode a
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Paragraph 0441; 0446; 0451; 0456
(2021/10/11)
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- Photocatalyst-Free, Visible-Light-Mediated C(sp3)-H Arylation of Amides via a Solvent-Caged EDA Complex
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A photocatalyst-free and mild visible light photochemical procedure for C(sp3)-H arylation of amides is described. The reaction proceeds via an electron donor-acceptor (EDA) complex between an electron-rich arene substrate and electron-poor persulfate oxi
- Kaur, Jaspreet,Shahin, Ahmed,Barham, Joshua P.
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supporting information
p. 2002 - 2006
(2021/03/08)
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- Immobilization of copper(II) into polyacrylonitrile fiber toward efficient and recyclable catalyst in Chan-Lam coupling reactions
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A series of polyacrylonitrile fiber (PANF)-supported copper(II) catalysts were prepared through the immobilization of Cu(II) into prolinamide-modified PANF (PANPA-2F) and subsequently used for the synthesis of diverse N-arylimidazoles from arylboronic acids and imidazole. The prepared Cu(II)@PANPA-2Fs were well characterized by mechanical strength, FT-IR, XRD, XPS and SEM. Among them, CuCl2@PANPA-2F exhibited excellent catalytic performance, and its activity was significantly affected by the Cu loading. This catalytic system also displayed good activity in the synthesis of N-arylsulfonamides from arylboronic acids and tosyl azide. It was highly efficient in gram-scale reactions and could be reused five times. The advantages of low cost, easy preparation, good durability and facile recovery make the fiber catalyst attractive.
- Zhang, Chenlu,Zhu, Hai,Gang, Kaiyue,Tao, Minli,Ma, Ning,Zhang, Wenqin
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- Cu(I)–N-heterocyclic carbene-catalyzed base free C–N bond formation of arylboronic acids with amines and azoles
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A new N-heterocyclic carbene (NHC) precursor of imidazolium chloride and its corresponding Cu(I)–NHC complex 1 was synthesized. The complex 1 was found to be a highly effective catalyst for Chan-Evans-Lam coupling of arylboronic acid with amines and azoles (including imidazole, pyrazole and triazole), without addition of base at room temperature. Various substituents on three substrates can be tolerated, giving the desired coupling products in good to excellent yields (62–94%). The method is practical and offers an alternative to the corresponding copper-catalyzed Chan-Evans-Lam process for the construction of C–N bonds.
- Zhang, Maoyuan,Xu, Zengbing,Shi, Dabin
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- Chitosan nanoparticles functionalized poly-2-hydroxyaniline supported CuO nanoparticles: An efficient heterogeneous and recyclable nanocatalyst for N-arylation of amines with phenylboronic acid at ambient temperature
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The present study aims to prepare an effective and eco-friendly nanocatalyst for the Chan–Lam coupling reaction of phenylboronic acid and amine in aerobic conditions. For this purpose, chitosan was extracted from shrimp shells waste by demineralization, deproteinization, and deacetylation processes and then converted to chitosan nanoparticles (CSN) by the ionic gelation with tripolyphosphate anions. Afterward, poly-2-hydroxyaniline (P2-HA) was grafted to chitosan nanoparticles (NPs) to employ as the support for CuO NPs. Characterization of the nanocatalyst was done using Fourier transform infrared (FT-IR), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), mapping, energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The CuO NPs were identified in the spherical shape with an average size of 17 nm. The prepared nanocatalyst exhibited excellent catalytic performance with a high turnover number (TON) and turnover frequency (TOF) for the Chan–Lam coupling reaction of phenyl boronic acid and amines with different electronic properties. The prepared catalyst could be readily recovered and reused for at least five runs without any noticeable change in structure and catalytic performance. Chitosan (CS) was prepared via demineralization, deproteinization, and deacetylation of shrimp shell and chitosan nanoparticles (CSN) were prepared via ionic gelation process. Polymerization of 2-HA on the CSN surface was done to increase functional groups and create active sites for CuO NPs attachments. CuO NPs-P2-HA-CSN nanocomposite has been shown high efficiently for the Chan–Lam coupling reaction.
- Seyedi, Neda,Zahedifar, Mahboobeh
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- Cu(OAc)2-porphyrins as an efficient catalytic system for base-free, nature mimicking Chan–Lam coupling in water
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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
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- Sustainable Synthesis of 2-Hydroxymethylbenzimidazoles using D-Fructose as a C2 Synthon
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D-fructose, a biomass-derived carbohydrate has been identified as an environmentally benign C2 synthon in the preparation of synthetically useful 2-hydroxymethylbenzimidazole derivatives by coupling with 1,2-phenylenediamines. Proof of concept was established by synthesizing 23 examples using BF3.OEt2 (20 mol%), TBHP (5.5 M, decane) (1.0 equiv.) in CH3CN at 90 °C for 1 h. The pivotal features of this method include metal-free conditions, short time, good functional group tolerance, gram scale feasibility and the synthesis of benzimidazole fused 1,4-oxazine. Control studies with conventional C2 synthons did not produce the desired product, thus suggesting a new reaction pathway from D-fructose.
- Raja, Dineshkumar,Philips, Abigail,Sundaramurthy, Devikala,Chandru Senadi, Gopal
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supporting information
p. 3754 - 3759
(2021/10/14)
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- Highly efficient one pot synthesis of benzimidazoles from 2-nitroaniline and PhSiH3 as reducing agent catalyzed by Pd/C as a heterogeneous catalyst
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This work reports an efficient route for the synthesis of benzimidazole from o-nitroaniline in the presence of carbon dioxide atmosphere, PhSiH3 as a reducing agent catalyzed by Pd/C as a catalyst. Benzimidazoles have become the focus of organic chemists, as benzimidazole is an important intermediate in medicinal chemistry. We have developed more efficient route for the synthesis benzimidazole and various substituted benzimidazoles have been synthesized in good to excellent yield. The TBD (1,5,7-Triazabicyclo [4.4.0] dec-5-ene) is selected as a base as it promotes the CO2 insertion. Benzimidazoles were synthesized through reduction of nitro group followed by cyclization of amine using CO2 as a carbon source. Moreover, the Pd/C catalyst can be recycled up to five recycle run without significant changes in the yield of the product.
- Phatake, Vishal V.,Bhanage, Bhalchandra M.
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- A Chemoselective and Desulfurative Chan–Lam Coupling: C–N Bond Formation between Benzimidazoline-2-Thiones and Arylboronic Acids
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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
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supporting information
p. 2414 - 2424
(2020/03/23)
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- A Highly Active, Recyclable and Cost-Effective Magnetic Nanoparticles Supported Copper Catalyst for N-arylation Reaction
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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
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- Bimetallic Bis-NHC-Ir(III) Complex Bearing 2-Arylbenzo[d]oxazolyl Ligand: Synthesis, Catalysis, and Bimetallic Effects
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Herein, an unprecedented bimetallic bis-NHC Cp*Ir complex 1 bearing 2-arylbenzo[d]oxazolyl and NHC ligands is reported. A significant increase in activity was observed for N-methylation of amines and reduction of aldehydes with MeOH catalyzed by 1 compared to the monometallic analogues (2-11). Under the optimal conditions, it showed to be highly effective in N-methylation of nitroarenes with MeOH as both C1 and H2 source. Substrates, including aromatic amines, ketones, and nitro compounds with various functional groups, can be well-tolerated. Mechanistic studies and DFT calculation highlight the significance of bimetallic centers cooperativity.
- Huang, Shuang,Hong, Xi,Cui, He-Zhen,Zhan, Bing,Li, Zhi-Ming,Hou, Xiu-Feng
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supporting information
p. 3514 - 3523
(2020/10/09)
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- Cu(i) based catalysts derived from bidentate ligands and studies on the effect of substituents for: N -arylation of benzimidazoles and indoles
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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
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supporting information
p. 19591 - 19597
(2020/12/05)
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- Halogen Bond-Catalyzed Povarov Reactions
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The use of a bidentate halogen bond donor to catalyse Povarov reactions of imines derived from aryl adehydes and anilines is reported. Dienophiles used in these reactions included 2,3-dihydrofuran, N-vinyl-2-pyrrolidone and N-Cbz-protected 2,3-dihydropyrr
- Liu, Xuelei,Toy, Patrick H.
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supporting information
p. 3437 - 3441
(2020/07/24)
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- Carbonylative Acetylation of Heterocycles
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Herein, a new procedure for the carbonylative acetylation of heterocycles has been developed. In this process, organic peroxide acts as the methyl source. Various heterocycles were transformed into the corresponding methyl heterocyclic ketones in moderate to good yields.
- Zhang, Youcan,Yin, Zhiping,Wu, Xiao-Feng
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supporting information
p. 213 - 216
(2020/01/22)
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- Tuning the Copper(II)/Copper(I) Redox Potential for More Robust Copper-Catalyzed C–N Bond Forming Reactions
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Complexes of copper and 1,10-phenanthroline have been utilized for organic transformations over the last 50 years. In many cases these systems are impacted by reaction conditions and perform best under an inert atmosphere. Here we explore the role the 1,1
- Biswas, Saborni,Cope, James D.,Emerson, Joseph P.,Goel, Ekta,Hall, Ruby S.,Hendrich, Michael P.,Riley, Kathleen M.,Stokes, Sean L.,Valle, Henry U.,Wipf, David O.
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supporting information
(2020/03/23)
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- Intercalation of copper salt to montmorillonite K-10 and its application as a reusable catalyst for Chan–Lam cross-coupling reaction
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A simple and efficient catalytic system has been developed by adsorption of copper salt in the interlayers of montmorillonite K-10. The catalytic system impressively exercises the green chemistry perspective leading to effortless recovery and recyclabilit
- Sarmah, Manashi,Dewan, Anindita,Boruah, Purna K.,Das, Manash R.,Bora, Utpal
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- Benzimidazole bearing Pd–PEPPSI complexes catalyzed direct C2-arylation/heteroarylation of N-substituted benzimidazoles
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A convenient and highly efficient palladium-catalyzed direct C2-arylation/heteroarylation of N-substituted benzimidazole derivatives such as N-benzyl/3-chlorobenzyl/2,4,6-trimethylbenzyl/2,4,6-triisopropylbenzyl/aryl benzimidazoles with various aryl/heter
- Gokanapalli, Anusha,Motakatla, Venkata Krishna Reddy,Peddiahgari, Vasu Govardhana Reddy
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- ORGANOMETALLIC COMPOUND AND ORGANIC LIGHT-EMITTING DEVICE INCLUDING THE SAME
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Provided are an organometallic compound represented by Formula 1 and an organic light-emitting device including the same. The organic light-emitting device includes a first electrode; a second electrode facing the first electrode; an organic layer between
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Paragraph 0375; 0376; 0391; 0392
(2020/10/20)
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- ORGANOMETALLIC COMPOUND AND ORGANIC LIGHT-EMITTING DEVICE INCLUDING THE SAME
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An organic light-emitting device includes: a first electrode; a second electrode facing the first electrode; and an organic layer between the first electrode and the second electrode, the organic layer including an emission layer. The emission layer includes at least one organometallic compound of Formula 1, and at least one selected from a second compound and a third compound, where the organometallic compound, the second compound, and the third compound are different from each other. When the emission layer comprises both the second compound and the third compound, the second compound and the third compound form an exciplex, and the organometallic compound and the second compound and/or the third compound do not form an exciplex: [in-line-formulae]M(L1)n1(L2)n2,??Formula 1[/in-line-formulae] wherein in Formula 1, L1 is represented by Formula 2-1:
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Paragraph 0404-0405; 0422-0423
(2020/11/22)
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- Metal-Free Synthesis of Benzimidazoles via Oxidative Cyclization of d -Glucose with o-Phenylenediamines in Water
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d-Glucose has been identified as an efficient C1 synthon in the synthesis of benzimidazoles from o-phenylenediamines via an oxidative cyclization strategy. Isotopic studies with 13C6-d-glucose and D2O unambiguously confirmed the source of methine. The notable features of this method include the following: broad functional group tolerance, a biorenewable methine source, excellent reaction yields, a short reaction time, water as an environmentally benign solvent, and the synthesis of vitamin B12 component on the gram scale.
- Raja, Dineshkumar,Philips, Abigail,Palani, Pushbaraj,Lin, Wei-Yu,Devikala, Sundaramurthy,Senadi, Gopal Chandru
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p. 11531 - 11540
(2020/10/12)
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- Visible-light-induced aerobic oxidative desulfurization of 2-mercaptobenzimidazolesviaa sulfinyl radical
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A mild transition-metal-free non-toxic aerobic photoredox system was found to enable highly efficient desulfurization of 2-mercaptobenzimidazoles. This viable catalytic system includes Rose Bengal in a low catalyst loading as a photosensitizer and cheap, non-toxic NaCl in a catalytic amount as an additive, combined with an oxygen atmosphere. This protocol provides an important alternative access to a broad range of benzimidazole and deuterated benzimidazole products in generally high yields with good tolerance of various synthetically and pharmaceutically useful functionalities. The mechanistic studies reveal that both single electron transfer and energy transfer probably occur in the initial step and a sulfinyl radical intermediate is involved in the key desulfurization process.
- Deng, Guo-Jun,Fu, Mei,Huang, Huawen,Ji, Xiaochen,Li, Yongtong
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supporting information
p. 5594 - 5598
(2020/09/21)
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- N -Arylation of (hetero)arylamines using aryl sulfamates and carbamates via C-O bond activation enabled by a reusable and durable nickel(0) catalyst
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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
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p. 13266 - 13278
(2020/10/07)
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- Transition-metal and oxidant-free approach for the synthesis of diverse N-heterocycles by TMSCl activation of isocyanides
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A highly efficient TMSCl-mediated addition of N-nucleophiles to isocyanides has been achieved. This transition-metal and oxidant-free strategy has been applied to the construction of various N-heterocyles such as quinazolinone, benzimidazole and benzothiazole derivatives by the use of distinct amino-based binucleophiles. The notable feature of this protocol includes its mild reaction condition, broad functional group tolerance and excellent yield. This journal is
- Chen, Fen-Er,Dong, Lin,Li, Hongyan,Liu, Jinxin,Luo, Liangliang,Xiao, You-Cai,Zhou, Yuan
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p. 29257 - 29262
(2020/10/02)
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- K2S as Sulfur Source and DMSO as Carbon Source for the Synthesis of 2-Unsubstituted Benzothiazoles
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We describe a three-component reaction of o-iodoanilines with K2S and DMSO that provides 2-unsubstituted benzothiazoles in moderate to good isolated yields with good functional group tolerance. Electron-rich aromatic amines and o-phenylenediamines instead of o-iodoanilines provided 2-unsubstituted benzothiazoles and 2-unsubstituted benzimidazoles with and without K2S under similar conditions. Notably, DMSO plays three vital roles: carbon source, solvent, and oxidant.
- Deng, Guobo,Kuang, Daizhi,Liang, Yun,Yang, Yuan,Yu, Jiangxi,Zhang, Fuxing,Zhu, Xiaoming
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supporting information
p. 3789 - 3793
(2020/06/04)
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- Synthesis method of ammonium acetate mediated benzimidazole compound
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The invention discloses a synthesis method of a benzimidazole compound mediated by ammonium acetate. The synthesis method comprises the following steps: adding an o-phenylenediamine compound, dimethylsulfoxide, an additive 1 and an additive 2 into a reaction tube, carrying out a stirring reaction at 130-150 DEG C, cooling the reaction product to room temperature after the reaction is finished, and carrying out separation and purification on the product to obtain the benzimidazole compound. The invention develops a method for synthesizing a benzimidazole compound under the mediation of ammonium acetate by taking DMSO as a carbon source and an oxidant and an o-phenylenediamine compound as a substrate under the condition of no metal catalyst. The synthesis method does not need a metal catalyst, and the required carbon source and oxidant have the characteristics of low toxicity, low price, easiness in obtaining, stable performance and the like. The method has the advantages of easiness inoperation, few steps, mild reaction conditions, better functional group tolerance and the like, and provides a new valuable way for synthesizing benzimidazole compounds.
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Paragraph 0066-0068
(2020/11/23)
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- Synthesis method of benzimidazole compound based on iron catalytic oxidation-reduction coupling reaction
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The invention belongs to the field of organic synthesis, and relates to a benzimidazole compound synthesis method based on an iron catalytic oxidation-reduction coupling reaction. According to the method, o-nitroaniline compounds and alcohol compounds are used as raw materials, and the benzimidazole compounds are generated through iron-catalyzed redox coupling reaction in the presence of an iron catalyst and a proton donor. The method provided by the invention provides a new way for the synthesis of benzimidazole drugs and pesticides. Compared with a traditional benzimidazole compound synthesis method with o-phenylenediamine compounds and carboxylic acid or carboxylic acid derivatives as raw materials, the method has the advantages that the atom utilization rate of the whole process is increased, the production cost is reduced, and waste gas, waste liquid and waste solid generated in the production process is reduced.
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Paragraph 0069-0073
(2020/10/05)
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- Highly-efficient N-arylation of imidazole catalyzed by Cu(II) complexes with quaternary ammonium-functionalized 2-acetylpyridine acylhydrazone
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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
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- 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
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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
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p. 323 - 334
(2019/11/05)
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- CNT-CuO catalyzed C–N bond formation for N-arylation of 2-phenylindoles
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Carbon nanotube–copper oxide (CNT–CuO) nanocomposites were prepared by depositing CuO nanoparticles onto functionalized CNT surfaces. The structure and elemental content of CNT–CuO were characterized using transmission electron microscopy, X-ray diffraction, and Auger electron spectroscopy. The prepared CNT-CuO was subsequently employed as a catalyst for the coupling reaction of 2-phenylindole with aryl iodides to provide the desired N-aryl 2-phenylindoles in good yields.
- Lim, Jeongah,Kim, Ji Dang,Choi, Hyun Chul,Lee, Sunwoo
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supporting information
(2019/10/14)
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- Iron-Catalyzed/Mediated C-N Bond Formation: Competition between Substrate Amination and Ligand Amination
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Iron catalyzed carbon-nitrogen bond formation reactions of a wide variety of nucleophiles and aryl halides using well-defined iron-complexes featuring redox noninnocent 2-(arylazo)-1,10-phenanthroline (L1) ligands are reported. Besides substrate centered C-N coupling, C-N bond formation reactions were also observed at the ortho- and para-positions of the phenyl ring of the coordinated azo-aromatic scaffolds affording new tetradentate ligands, 2-N-aryl-(2-arylazo)-1,10-phenanthroline (L2), and tridentate ligands, 4-N-aryl-(2-arylazo)-1,10-phenanthroline (L3), respectively. Control experiments and mechanistic studies reveal that the complex [FeL1Cl2] (1) undergoes in situ reduction during the catalytic reaction to produce the monoanionic complex [1]-, which then acts as the active catalyst. The metal (iron) and the coordinated ligand were found to work in a cooperative manner during the transfer processes involved in the fundamental steps of the catalytic cycle. Detailed experimental and theoretical (DFT) studies were performed to get insight into the competitive substrate versus ligand centered amination reactions.
- Sinha, Suman,Sikari, Rina,Sinha, Vivek,Jash, Upasona,Das, Siuli,Brand?o, Paula,Demeshko, Serhiy,Meyer, Franc,De Bruin, Bas,Paul, Nanda D.
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p. 1935 - 1948
(2019/01/25)
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- Halogen Bond-Catalyzed Friedel-Crafts Reactions of Aldehydes and Ketones Using a Bidentate Halogen Bond Donor Catalyst: Synthesis of Symmetrical Bis(indolyl)methanes
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The use of a halogen bond donor to catalyze Friedel-Crafts reactions of indoles with a range of aldehydes and ketones to directly produce bis(indolyl)methanes, including the natural products arsindoline A, arundine, trisindoline, and vibrindole A, is reported. The bidentate catalyst used in these reactions proved to be more effective than a monondentate analogue, a thiourea commonly used as an organocatalyst, and even a trityl cation that has been used previously in the synthesis of bis(indolyl)methanes.
- Liu, Xuelei,Ma, Shuang,Toy, Patrick H.
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supporting information
p. 9212 - 9216
(2019/11/14)
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- Preparation method of diarylamine compound
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The invention relates to a preparation method of a diarylamine compound. Specifically, under the catalysis of cuprous oxide supported by chitosan, the arylation reaction used for a nitrogen-containingheterocyclic compound is achieved, and the corresponding diarylamine compound is obtained. The preparation method of the diarylamine compound has the advantages that the process conditions are simple, the yield is good, the operability is strong, and the functional group tolerance is wide.
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Paragraph 0070; 0071; 0072
(2019/04/26)
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- Efficient N-arylation of azole compounds utilizing selective aryl-transfer TMP-iodonium(III) reagents
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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
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p. 1281 - 1286
(2019/04/10)
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- Copper-Catalyzed NaBAr 4-Based N-Arylation of Amines
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Using NaBAr 4 as an arylating agent, the formation of carbon-heteroatom bonds by a Cham-Lam cross-coupling reaction in the presence of catalytic copper(II) acetate monohydrate in acetonitrile at room temperature under air is described. The investigation of reaction scope suggests that several aliphatic and aromatic amines are compatible. In particular, the reaction of alkylamine and NaBAr 4 proceeds smoothly to offer the corresponding products in good to excellent yields.
- Yang, Qin,Lei, Xiaoli,Yin, Zhijian,Deng, Zhihong,Peng, Yiyuan
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supporting information
p. 538 - 544
(2019/01/10)
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- In Situ Formation of Frustrated Lewis Pairs in a Water-Tolerant Metal-Organic Framework for the Transformation of CO2
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Frustrated Lewis pairs (FLPs) consist of sterically hindered Lewis acids and Lewis bases, which provide high catalytic activity towards non-metal-mediated activation of “inert” small molecules, including CO2 among others. One critical issue of homogeneous FLPs, however, is their instability upon recycling, leading to catalytic deactivation. Herein, we provide a solution to this issue by incorporating a bulky Lewis acid-functionalized ligand into a water-tolerant metal-organic framework (MOF), named SION-105, and employing Lewis basic diamine substrates for the in situ formation of FLPs within the MOF. Using CO2 as a C1-feedstock, this combination allows for the efficient transformation of a variety of diamine substrates into benzimidazoles. SION-105 can be easily recycled by washing with MeOH and reused multiple times without losing its identity and catalytic activity, highlighting the advantage of the MOF approach in FLP chemistry.
- Shyshkanov, Serhii,Nguyen, Tu N.,Ebrahim, Fatmah Mish,Stylianou, Kyriakos C.,Dyson, Paul J.
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supporting information
p. 5371 - 5375
(2019/03/17)
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- Cobalt-catalyzed synthesis of N-containing heterocycles: Via cyclization of ortho -substituted anilines with CO2/H2
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The CO2-involved synthesis of chemicals is of great significance from the green and sustainable chemistry viewpoint. Herein, we report a non-noble metal catalytic system composed of CoF2, CsF and P(CH2CH2PPh2)3 (denoted as PP3) for the synthesis of N-containing heterocycles from ortho-substituted anilines and CO2/H2. Mechanism investigation indicates that [Co(PP3)H(CO2)]+ is a catalytically active intermediate under working conditions; and CsF plays important roles in activating ortho-substituted anilines via hydrogen bond interactions, thus promoting the formation of the final products. This catalytic system is highly efficient, and allows a wide scope of ortho-substituted anilines, together with excellent functional group tolerance, affording various N-containing heterocycles in good to excellent yields.
- Ke, Zhengang,Yu, Bo,Wang, Huan,Xiang, Junfeng,Han, Juanjuan,Wu, Yunyan,Liu, Zhenghui,Yang, Peng,Liu, Zhimin
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p. 1695 - 1701
(2019/04/10)
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- 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
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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
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- Copper(I)-USY as a Ligand-Free and Recyclable Catalyst for Ullmann-Type O-, N-, S-, and C-Arylation Reactions: Scope and Application to Total Synthesis
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The copper(I)-doped zeolite CuI-USY proved to be a versatile, efficient, and recyclable catalyst for various Ullmann-type coupling reactions. Easy to prepare and cheap, this catalytic material enables the arylation and heteroarylation of diverse O-, N-, S-, and C-nucleophiles under ligand-free conditions while exhibiting large functional group compatibility. The facility of this catalyst to promote C-O bond formation was further demonstrated with the total synthesis of 3-methylobovatol, a naturally occurring diaryl ether of biological relevance. From a mechanistic viewpoint, two competitive pathways depending on the nature of the nucleophile and consistent with the obtained results have been proposed.
- Garnier, Tony,Danel, Mathieu,Magné, Valentin,Pujol, Anthony,Bénéteau, Valérie,Pale, Patrick,Chassaing, Stefan
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p. 6408 - 6422
(2018/05/31)
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- Optimization of diarylpentadienones as chemotherapeutics for prostate cancer
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Our earlier studies indicate that (1E,4E)-1,5-bis(1-alkyl-1H-imidazol-2-yl)penta-1,4-diene-3-ones and (1E,4E)-1,5-bis(1-alkyl-1H-benzo[d]imidazol-2-yl)penta-1,4-diene-3-ones exhibit up to 121-fold greater antiproliferative potency than curcumin in human p
- Patanapongpibul, Manee,Zhang, Changde,Chen, Guanglin,Guo, Shanchun,Zhang, Qiang,Zheng, Shilong,Wang, Guangdi,Chen, Qiao-Hong
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p. 4751 - 4760
(2018/08/21)
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- 2,6-Bis(2-methylhydrazine-1-carbonyl)pyridine 1-oxide as an Efficient Ligand for Copper-Catalyzed C–N Coupling Reaction in Water
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Abstract: Cu2O/2,6-bis(2-methylhydrazine-1-carbonyl)pyridine 1-oxide was found to be an efficiently catalytic system for the N-arylation of imidazole, indole, benzimidazole, pyrrole, benzylamine and ethanolamine with aryl iodides and bromides by using NaOH as base in the presence of 20?mol% (n-Bu)4NBr, and water as solvent at 130?°C in 24?h, and giving the N-arylated products in moderate to excellent yields.
- Wang, Xiaochuang,Meng, Fei,Zhang, Jie,Xie, Jianwei,Dai, Bin
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p. 1142 - 1149
(2018/02/22)
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- N, O-Bidentate ligand-tunable copper(II) complexes as a catalyst for Chan-Lam coupling reactions of arylboronic acids with 1 H-imidazole derivatives
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An efficient procedure for Chan-Lam coupling reactions of arylboronic acids with 1H-imidazole derivatives using N,O-bidentate ligand-tunable copper(ii) complexes as a catalyst under base-free conditions has been developed. This protocol features mild reac
- Jia, Xuefeng,Peng, Pai
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p. 8984 - 8988
(2018/12/10)
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- Chan-Lam cross-coupling reaction based on the Cu2S/TMEDA system
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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
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p. 606 - 617
(2018/01/01)
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