- Palladium-catalyzed amination of aryl bromides and aryl triflates using diphosphane ligands: A kinetic study
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[Pd(P-O-P)(Ar)]+ complexes with ligands that have wide bite angles are active catalysts for the coupling of aniline derivatives with aryl triflates. Kinetic studies show that for these systems a fast equilibrium that involves coordination of the amine precedes the deprotonation, which is the rate-limiting step of the reaction. This reaction is faster for compounds with a smaller P-Pd-P angle. When halide salts are present, the base sodium tert-butoxide is activated and adds to the palladium complex. This rate-limiting step is preceded by a fast equilibrium that involves decoordination of the halide. The initial reaction rate is faster for compounds with a larger P-Pd-P angle. This is due to the closer proximity of the oxygen to the Pd center, and this assists in the dissociation of the halide.
- Guari, Yannick,Van Strijdonck, Gino P. F.,Boele, Maarten D. K.,Reek, Joost N. H.,Kamer, Paul C. J.,Van Leeuwen, Piet W. N. M.
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- Antioxidant activities of phenothiazines and related compounds: Correlation between the antioxidant activities and dissociation energies of O-H or N-H bonds
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The antioxidant activities of phenothiazines, carbazoles, and related diphenylamines were evaluated in the oxidation of tetralin at 60°C and linoleic acid micelles in aqueous dispersion at 37°C induced by an azo initiator. Phenothiazines were highly antioxidant in both systems. Although diphenylamine and carbazole were not good antioxidants, those having a hydroxy group as a substituent at the ortho or para position to the amino group were potently antioxidant. The antioxidant activity of o-hydroxydiphenylamine was much greater than that of other compounds in both systems due to a stabilization of the phenoxyl radical by delocalization of the unpaired electron to the p-type lone pair of the amino group. A semiempirical MNDO-AM1 calculation was applied to study hydrogen abstractions of antioxidants in the chain process of autoxidation. These results indicated that the rates of oxidation during the induction period correlated with the dissociation energies of the O-H or N-H bonds.
- Yamamura, Tatsuo,Suzuki, Kyouichi,Yamaguchi, Tatsuya,Nishiyama, Tomihiro
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- Pd-catalyzed amination in a polar medium: Rate enhancement, convenient product isolation, and tandem Suzuki cross-coupling
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A catalytic system utilizing a polar medium for the Pd-catalyzed amination reaction is described. This system utilizes Pd[P(t-Bu)3]2 and a weak base and displays a modest rate enhancement compared to similar existing protocols. Significant functional group tolerance is observed in both amine and aryl halide, including carboxylates, carbamates, nitriles, amides, and esters. Product isolation after filtration and automated reverse-phase chromatography readily permits parallel synthetic approaches if desired.
- Stauffer, Shaun R.,Steinbeiser, Melissa A.
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- Circularly polarized luminescence from bridged triarylamine helicenes
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The first examples of circularly polarized luminescence from chiral bridged triarylamine-based heterohelicene molecules are reported. The luminescence dissymmetry factors are ~ |0.001|. Copyright
- Field, Jason E.,Muller, Gilles,Riehl, James P.,Venkataraman
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- The synthesis of a [2.2]paracyclophane-derived secondary phosphine oxide and a study of its reactivity
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A planar chiral secondary phosphine oxide based on [2.2]paracyclophane was synthesized and its chemistry investigated; it was shown to be a competent pre-ligand in palladium(0)-mediated reactions, and displayed promising activity in gold(I)-catalysed cyclisations. The secondary phosphine oxide could be transformed into a collection of P-stereogenic tertiary phosphine oxides. These are rare examples of the planar chirality of [2.2]paracyclophane being combined with a P-stereogenic centre. Unfortunately, epimerisation of the phosphorus stereocentre during reduction limits the use of this chemistry.
- Mungalpara, Maulik N.,Wang, Jingjing,Coles, Martyn P.,Plieger, Paul G.,Rowlands, Gareth J.
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- Solvent free amination reactions of aryl bromides at room temperature catalyzed by a (π-allyl)palladium complex bearing a diphosphinidenecyclobutene ligand
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An air- and moisture-stable (π-allyl)palladium complex bearing a unique diphosphinidenecyclobutene ligand effectively catalyzes amination reactions of aryl bromides with amines, where the reactions proceed under mild conditions without solvent, with 2 mol % of catalyst and 1 equiv of t-BuOK at room temperature. Under these conditions the amination products were obtained in good to excellent isolated yields.
- Gajare, Anil S.,Toyota, Kozo,Yoshifuji, Masaaki,Ozawa, Fumiyuki
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- Antioxidant effects of the hydroxy groups in the simple phenolic carbazoles
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Antioxidant activities of the simple phenolic carbazoles 5-11 were evaluated by 2,2-diphenyl-1-picrylhydrazyl and 2,2′-azinobis-(3-ethylbenzthiazoline-6-sulfonate)+ radical scavenging assays. The simple phenolic carbazoles 5-7, 9, and 11 exhibited stronger antioxidant activities than α-tocopherol, and similar antioxidant activities as phenolic carbazole alkaloids carazostatin (1), and carbazomadurins A (3) and B (4). Bond dissociation energies and highest occupied molecule orbital energy levels of a series of phenolic carbazoles including phenolic carbazole alkaloids were calculated. The reducing ability of the phenolic carbazole core could be important role for the antioxidant activity of carbazole alkaloids 1, 3, and 4.
- Hieda, Yuhzo,Hatae, Noriyuki,Anraku, Makoto,Matsuura, Nobuyasu,Uemura, Kazuhide,Hibino, Satoshi,Choshi, Tominari,Tomida, Hisao,Hori, Osamu,Fujioka, Haruto
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- Diastereoselective Allylation of Aldehydes by Dual Photoredox and Chromium Catalysis
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Herein, we report the redox-neutral allylation of aldehydes with readily available electron-rich allyl (hetero-) arenes, β-alkyl styrenes and allyl-diarylamines. This process was enabled by the combination of photoredox and chromium catalysis, which allowed a range of homoallylic alcohols to be prepared with high levels of selectivity for the anti diastereomer. Mechanistic investigations support the formation of an allyl chromium intermediate from allylic C(sp3)-H bonds and thus significantly extends the scope of the venerable Nozaki-Hiyama-Kishi reaction.
- Schwarz, J. Luca,Sch?fers, Felix,Tlahuext-Aca, Adrian,Lückemeier, Lukas,Glorius, Frank
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- N-Heterocyclic Carbene Palladium(II) Amine Complexes: The Role of Primary Aryl- or Alkylamine Binding and Applications in the Buchwald-Hartwig Amination Reaction
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N-heterocyclic carbene-palladium(II) amine complexes bearing primary aryl- or alkylamines were synthesized. The prepared complexes were characterized by single crystal X-ray diffraction as well as NMR spectroscopy. These complexes exhibited good catalytic activities for the Buchwald-Hartwig amination reaction of aryl chlorides to afford arylated anilines under mild conditions. All reactions were carried out in air and all starting materials were used as supplied without purification. 21 expected coupling products were obtained in moderate to high yields under optimum conditions.
- Hsu, Yu-Cheng,Chen, Ming-Tsz
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supporting information
(2021/12/24)
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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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- 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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- A quinoxaline-based porous organic polymer containing copper nanoparticles CuNPs@Q-POP as a robust nanocatalyst toward C-N coupling reaction
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A novel porous organic polymer (denoted by Q-POP) was successfully fabricated by free-radical copolymerization of allyl-substituted 2,3-di(2-hydroxyphenyl)1,2-dihydroquinoxaline, and divinylbenzene under solvothermal conditions and used as a new platform for immobilization of copper nanoparticles. The CuNPs@Q-POP nanocatalyst was prepared via incorporating of Cu(NO3)2 into the polymeric network, followed by the reduction of Cu2+ ion with hydrazine hydrate. The obtained materials were characterized through FT-IR, XRD, N2 adsorption-desorption isotherms, ICP, TGA, SEM, HR-TEM, EDX, and the single-crystal X-ray crystallography. The results displayed that Q-POP and CuNPs@Q-POP possessed high surface area, hierarchical porosity, and excellent thermal and chemical stability. The as-synthesized catalyst was utilized for the Ullmann C-N coupling reaction of aromatic amines and different aryl halides to prepare various diarylamine derivatives. All types of aryl halides (except aryl fluorides) were screened in the Ullmann C-N coupling reaction with aromatic amines to produce diaryl amines in good to excellent yields (50-98%), and it turned out that aryl iodides have the best results. Besides, due to the strong interactions between CuNPs, N, and O-atoms of quinoxaline moiety existing in the polymeric framework, the copper leaching from the support was not observed. Furthermore, the catalyst was recycled and reused for five consecutive runs without significant activity loss.
- Gorginpour, Forough,Zali-Boeini, Hassan,Rudbari, Hadi Amiri
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p. 3655 - 3665
(2021/02/03)
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- One-pot synthesis of symmetrical and asymmetrical diphenylamines from guanidines with aryl iodide using Cu/Cu2O nanocatalyst
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This work reports the selective one-pot synthesis of symmetrical and asymmetrical amines from guanidines as ammonia surrogate. The use of guanidine as ammonia source will eliminate the need of handling liquid ammonia. The reaction was performed using Cu/Cu2O nanocatalyst under ligand-free condition. The synthesized catalyst was characterized by a various technique like XRD, FEG-SEM, HRTEM and XPS. The different diphenylamines are produced in good to very good yields. Recyclability study of catalyst shows that up to five cycles there is no significant loss in its activity.
- Chaurasia, Shivkumar R.,Bhanage
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- Copper(I)–creatine complex on magnetic nanoparticles as a green catalyst for N- and O-arylation in deep eutectic solvent
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Immobilization of copper(I) ions on magnetic nanoparticles was performed using surface modification of Fe3O4 with creatine. Fe3O4?creatine-Cu(I) magnetic catalyst was synthesized and applied in C&bond;X cross-coupling reactions with aryl halides in a deep eutectic as a green solvent. The results indicate the Fe3O4?creatine-Cu(I) magnetic nanoparticles showed excellent activity and high stability. In addition, it was revealed that this catalyst can be recycled five times without significant loss in catalytic activity.
- Bagheri, Sepideh,Heydari, Akbar,Pazoki, Farzane,Radfar, Iman
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- A new copper complex on graphene oxide: A heterogeneous catalyst for N-arylation and C-H activation
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Graphene oxide supported Cu (II) ligand complex (GO?AP/L-Cu) has been synthesized and characterized by FT-IR, Raman, PXRD, UV–Visible, TGA, XPS, FESEM, TEM, EDAX, Elemental mapping, BET, CHNS and AAS analysis. The complex has been found to be efficient and reusable heterogeneous catalyst for the N-arylation and C-H activation reactions, both the catalytic reactions were found to be simple, cleaner and give high yields (~ 90%) of product. The catalyst can be easily filtered out from the reaction mixture and reused up to four times without significant loss of catalytic activity. The reported method is economical and novel in the sense that aqueous medium was used for both the reactions and for the stability of the catalyst. All isolated organic products were fully characterized on the basis of their physical and spectral data.
- Mittal, Ayushi,Kumari, Shweta,Parmanand,Yadav, Deepak,Sharma, Sunil K.
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- Palladium-Catalyzed Synthesis of Benzophenanthrosilines by C?H/C?H Coupling through 1,4-Palladium Migration/Alkene Stereoisomerization
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A new and efficient synthesis of 8H-benzo[e]phenanthro[1,10-bc]silines from 2-((2-(arylethynyl)aryl)silyl)aryl triflates under palladium catalysis has been developed. The reaction mechanism was experimentally investigated and a catalytic cycle involving C
- Choi, Seung-Min,Kawakami, Yuka,Shintani, Ryo,Tsuda, Tomohiro
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supporting information
p. 8057 - 8061
(2020/03/19)
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- Peptide Nanofiber Templated Zinc Oxide Nanostructures as Non-precious Metal Catalyzed N-Arylation of Amines, One-Pot Synthesis of ImidazoHeterocycles and Fused Quinazolines
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In the present study, peptide nanofiber was used to immobilize zinc oxide. This nanoparticle was prepared through self-assembly in an aqueous solution. The structural properties of the prepared catalyst were examined by a series of techniques, such as FT-IR, EDS, SEM, TEM, XRD, ICP-OES (inductively coupled plasma optical emission spectrometry), and ultraviolet–visible (UV–Vis) spectroscopy. TEM images showed the necklace model for peptide nanofiber decorated with zinc oxide. The versatility of the method was investigated by N-arylation using reaction of amines with hydroxybenzotriazole as a novel phenylating reagent, one-pot synthesis of imidazoheterocycles by a three-component reaction of 2-aminopyridine, aldehyde, terminal alkyne and preparation of tetracyclic quinazolinone ring by one-pot reaction of isatoic anhydride, amine, and ninhydrin. High yields, low cost of catalyst, environmental friendliness, efficient recovery and recyclability of catalyst are the most important features of this catalytic system.
- Taherinia, Zahra,Ghorbani-Choghamarani, Arash,Hajjami, Maryam
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p. 151 - 168
(2018/10/26)
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- Copper-catalyzed, ceric ammonium nitrate mediated N-arylation of amines
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Cu-Catalyzed, ligand- and base-free cross-coupling of aryl boronic acids with primary and secondary amines has been reported. This ‘Chan-Evans-Lam' reaction has revealed that at room temperature, with a catalytic amount of copper(ii) acetate and ceric ammonium nitrate (CAN) as an oxidant, N-arylation can result in an effective C-N bond formation. This air stable, practical, robust protocol enables tolerance towards a variety of functional groups on both boronic acid and amine partners.
- Gonela, Uma Maheshwar,Ablordeppey, Seth Y.
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supporting information
p. 2861 - 2864
(2019/02/17)
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- Fe3O4@SiO2-copper sucrose xanthate as a green nanocatalyst for N-, O- and S-arylation
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Formation of C(sp2)–X bonds was carried out using a Fe3O4@SiO2-copper(I) sucrose xanthate nanoparticle catalyst with the aid of the copper(I) xanthate moiety in the catalyst which was prepared from the reaction between sucrose and carbon disulfide through an alkaline medium via the traditional Zeise approach. Various techniques were employed for the characterization of these novel nanoparticles. Three sorts of heteroatoms, N, O and S, successfully underwent heteroatom arylation to produce secondary or tertiary amines, ethers and thioethers, respectively.
- Radfar, Iman,Kazemi Miraki, Maryam,Esfandiary, Naghmeh,Ghandi, Leila,Heydari, Akbar
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- Diamines as interparticle linkers for silica-titania supported PdCu bimetallic nanoparticles in Chan-Lam and Suzuki cross-coupling reactions
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A series of highly efficient amine functionalized SiO2-TiO2 supported bimetallic PdCu catalysts with varied metal composition have been synthesized. Ethane-1,2-diamine, butane-1,4-diamine and hexane-1,6-diamine were employed as interparticle linkers for amine functionalization of a SiO2-TiO2 support material so as to study the effect of pendant chain length on stabilization and immobilization of bimetallic nanoparticles. The shortest carbon chain length on the support provided the best results, which may be due to the trapping of metal nanoparticles more efficiently by the basic nitrogen sites. The catalytic activities of these materials were evaluated for C-N and C-C coupling reactions. The most active catalyst, Pd1Cu1@12DA-STS, was characterized by various techniques including SEM, HR-TEM, ICP-AES, XRD, FTIR, EDX, CHN analysis and TGA studies. Moreover, the synthesized catalyst was found to be recyclable for up to five runs without significant loss of activity.
- Jamwal, Babita,Kaur, Manpreet,Sharma, Harsha,Khajuria, Chhavi,Paul, Satya,Clark
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p. 4919 - 4928
(2019/03/26)
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- A Polystyrene-Cross-Linking Tricyclohexylphosphine: Synthesis, Characterization and Applications to Pd-Catalyzed Cross-Coupling Reactions of Aryl Chlorides
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A polystyrene-cross-linking tricyclohexylphosphine (PS-TCP) was synthesized through radical emulsion polymerization of 4-tert-butylstyrene as a monomer and tris(trans-4-styrylcyclohexyl)phosphine as a threefold cross-linker. The PS-TCP showed enhanced ligand performance compared to the corresponding polystyrene-triphenylphosphine hybrid PS-TPP and tricyclohexylphosphine in Pd-catalyzed Suzuki–Miyaura and Buchwald–Hartwig reactions of aryl chlorides.
- Arashima, Junya,Iwai, Tomohiro,Sawamura, Masaya
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supporting information
p. 411 - 415
(2019/02/03)
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- Palladium-Catalyzed Amidation and Amination of (Hetero)aryl Chlorides under Homogeneous Conditions Enabled by a Soluble DBU/NaTFA Dual-Base System
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The palladium-catalyzed coupling of aryl and heteroaryl chlorides with primary amides under mild homogeneous reaction conditions is reported. Successful C-N coupling is enabled by the use of a unique "dual-base" system consisting of DBU and NaTFA, which serve as proton acceptor and halide scavenger, respectively, using low catalyst loadings (0.5 mol %) with readily available, air-stable palladium precatalysts. The DBU/NaTFA system also enables the room-temperature coupling of primary aryl amines with aryl chlorides and is tolerant of a variety of base-sensitive functional groups.
- Beutner, Gregory L.,Coombs, John R.,Green, Rebecca A.,Inankur, Bahar,Lin, Dong,Qiu, Jun,Roberts, Frederick,Simmons, Eric M.,Wisniewski, Steven R.
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supporting information
p. 1529 - 1537
(2019/09/04)
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- Recyclable bimetallic CuMoO4 nanoparticles for C-N cross-coupling reaction under mild conditions
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Herein we disclosed inexpensive copper(ii) bimetallic CuMoO4 nanoparticles for the C-N cross-coupling reaction of alkyl and aryl amines with haloarenes. The reaction proceeds under mild and ligand free conditions. The catalyst is recyclable and effective for a wide range of amines and haloarenes. Here, the efficiency of the Cu(ii) catalyst is increased by doping molybdenum metal. The bimetallic nanoparticles are anticipated to proceed via normal oxidative addition and reductive eliminations.
- Panigrahi, Reba,Panda, Subhalaxmi,Behera, Pradyota Kumar,Sahu, Santosh Kumar,Rout, Laxmidhar
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supporting information
p. 19274 - 19278
(2019/12/24)
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- Copper immobilized at a covalent organic framework: An efficient and recyclable heterogeneous catalyst for the Chan-Lam coupling reaction of aryl boronic acids and amines
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A polyimide covalent organic framework (PI-COF) with high thermal and chemical stabilities has been readily prepared from commercially available and inexpensive reagents and was employed as an effective support for heterogeneous copper. It was demonstrated that the obtained Cu@PI-COF is a highly active heterogeneous catalyst which can effectively promote the Chan-Lam coupling reaction of aryl boronic acids and amines in an open flask without the aid of any base or additive. In addition, the catalyst could be readily recovered from the reaction mixture by simple filtration and reused for at least eight cycles without any observable change in structure and catalytic activity.
- Han, Yi,Zhang, Mo,Zhang, Ya-Qing,Zhang, Zhan-Hui
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p. 4891 - 4900
(2018/11/21)
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- Synthesis of Di(hetero)arylamines from Nitrosoarenes and Boronic Acids: A General, Mild, and Transition-Metal-Free Coupling
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The synthesis of di(hetero)arylamines by a transition-metal-free cross-coupling between nitrosoarenes and boronic acids is reported. The procedure is experimentally simple, fast, mild, and scalable and has a wide functional group tolerance, including carbonyls, nitro, halogens, free OH and NH groups. It also permits the synthesis of sterically hindered compounds.
- Roscales, Silvia,Csák?, Aurelio G.
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supporting information
p. 1667 - 1671
(2018/03/23)
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- Palladium-catalyzed amination of aryl sulfoxides
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Amination of diaryl sulfoxides with anilines and alkylamines has been accomplished under palladium/N-heterocyclic carbene (NHC) catalysis. Owing to its electron deficiency, the leaving arenesulfenate anion would be smoothly released from the palladium center to result in uneventful catalyst turnover under milder reaction conditions in comparison with previous C-S bond amination reactions. This amination accommodated a wider range of functional groups such as silyl, boryl, methylsulfanyl, and halogen moieties. Regioselective amination of unsymmetrical diaryl sulfoxides was also executed by means of steric bias.
- Yoshida, Yuto,Otsuka, Shinya,Nogi, Keisuke,Yorimitsu, Hideki
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supporting information
p. 1134 - 1137
(2018/02/23)
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- Immobilization of nickel ions onto the magnetic nanocomposite based on cross-linked melamine groups: Effective heterogeneous catalyst for N-Arylation of Arylboronic acids
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A new magnetic heterogeneous catalyst was synthesized by immobilization of nickel ions onto a cross-linked polymeric nanocomposite composed of cyanuric chloride, ethylenediamine and functionalized magnetic nanoparticles. The resulting nitrogen rich support was capable of adsorbing large amounts of nickel ions (1.20 mmol g?1). The synthesized catalyst was characterized using AAS, TEM, FT-IR, EDX, TGA, SEM, BET and XRD techniques. The performance of the prepared catalyst was investigated in the C-N coupling of arylamines with aryl boronic acids. The reaction was carried out under a mild condition and good to moderate to good yields of products was obtained using only 5.0 mol% of the catalyst. The catalyst was easily recovered and reused for at least 7 times without any significant loss of its activity.
- Pourjavadi, Ali,Keshavarzi, Nahid,Moghaddam, Firouz Matloubi,Hosseini, Seyed Hassan
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- An Effective Heterogeneous Copper Catalyst System for C-N Coupling and Its Application in the Preparation of 2-Methyl-4-methoxydiphenylamine (MMDPA)
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A ligand-recyclable, environmentally benign heterogeneous catalyst system composed of CuI and polystyrene-supported N (-(4-(aminomethyl)naphthalen-1-yl)- N (-phenyl-1 H -pyrrole-2-carbohydrazide (PSAP) has been established for Ullmann type C-N coupling based on the homogeneous catalyst system N ′, N ′-diphenyl-1 H -pyrrole-2-carbohydrazide/CuI. This heterogeneous catalyst system maintained the catalytic effectiveness of the homogeneous catalyst. A variety of functionalized aryl bromides can be efficiently aminated with aryl amines and aliphatic amines with high selectivity for amines over alcohols. Moreover, a practical application of this catalyst system to promote the reaction of commercially available 4-methoxy-2-methylaniline and bromobenzene in 10 mmol scale, provided 2-methyl-4-methoxydiphenylamine (MMDPA) with 93% yield with the merit of the approach being simple operation for work-up and purification.
- Yi, Zhou,Huang, Manna,Wan, Yiqian,Zhu, Xinhai
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p. 3911 - 3920
(2018/09/29)
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- Pyrene-containing compound, preparation method thereof and organic light-emitting device
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The invention provides a pyrene-containing compound which has a structure as shown in formula 1 (FORMULA referring to the description), wherein X1 and X2 are oxygen (O) or sulfur (S); Y1 and Y2 are carbon (C) or nitrogen (N); and L1 is 0 or 1; and R1 and
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Paragraph 0024; 0025
(2018/11/22)
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- Nickel Dual Photoredox Catalysis for the Synthesis of Aryl Amines
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In this work, a new dual photoredox nickel catalysis system has been utilized for the synthesize of aryl amines. Previously, our group has shown that a nickel catalyst in conjunction with a photosensitizer and a sacrificial electron donor can cross-couple C-C bonds via photoredox-assisted reductive coupling. Here we have built upon that system to develop a redox-neutral cross-coupling system for the formation of C-N bonds. The catalytic system is composed of just a nickel cross-coupling catalyst, a Ru photocatalyst, and base and is capable of coupling amines with aryl halides in good to excellent yields. Furthermore, it was found that these reactions are functional under ambient conditions with catalyst loadings of 1 mol %. Spectroscopic studies provide support that this amination mechanism proceeds via a nitrogen-based radical intermediate. This N-radical mechanism offers direct synthetic access to di- and triaryl amines from nickel photocatalysis.
- Key, Ryan J.,Vannucci, Aaron K.
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p. 1468 - 1472
(2018/05/23)
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- Room-Temperature CuI-Catalyzed Amination of Aryl Iodides and Aryl Bromides
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A general and effective CuI/N′,N′-diaryl-1H-pyrrole-2-carbohydrazide catalyst system was developed for the amination of aryl iodides and bromides at room temperature with good chemoselectivity between -OH and -NH2 groups. Only 5 mol % of CuI and ligands was needed in this protocol to effect the amination of various aryl bromides and aryl iodides with a wide range of aliphatic and aryl amines (1.3 equiv).
- Ding, Xiaomei,Huang, Manna,Yi, Zhou,Du, Dongchen,Zhu, Xinhai,Wan, Yiqian
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p. 5416 - 5423
(2017/05/25)
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- The first report on the preparation of peptide nanofibers decorated with zirconium oxide nanoparticles applied as versatile catalyst for the amination of aryl halides and synthesis of biaryl and symmetrical sulfides
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We have reported the preparation of peptide nanofibers decorated with zirconium oxide nanoparticles for the first time as a novel, non-toxic, inexpensive and recyclable catalyst for the amination of aryl halides and synthesis of biaryl and symmetrical sulfides (via reaction of aryl halides with S8 or 2-thiobarbituric acid as sulfur transfer reagents). The structure of the catalyst was studied by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), atomic absorption spectroscopy (AAS), UV-visible absorption and fluorescence spectroscopy.
- Ghorbani-Choghamarani, Arash,Taherinia, Zahra
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p. 9414 - 9423
(2017/08/29)
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- The invention relates to a N, N - disubstituted hydrazide as ligand copper catalysis C - N coupling method (by machine translation)
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The invention discloses a to N, N - disubstituted hydrazide as ligand copper catalysis C - N coupling method, the method uses the aromatic halides with amine compound as a raw material, in order to alcohol compound as the solvent, in order to copper or copper compound as a catalyst, in order to as formula I or formula II as shown by a N, N - disubstituted hydrazide as a ligand, the presence of a base, in the 10 - 130 °C generating C - N coupled reaction for generating N - aryl compound: the invention mild reaction conditions, high chemical selectivity, substrate and wide range of application, simplicity of operation, product is simple and easy to separation and environmental protection, the obtained product yield is higher. Wherein R1, R2 is selected from methyl, phenyl, 4 - methoxyphenyl, 4 - nitro-phenyl, 2 - methylphenyl, 2 - isopropyl phenyl; R3 is hydrogen or methoxy. (by machine translation)
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Paragraph 0039-0041
(2017/07/21)
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- Molecular Adsorbates Switch on Heterogeneous Catalysis: Induction of Reactivity by N-Heterocyclic Carbenes
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We report the N-heterocyclic carbene (NHC)-induced activation of an otherwise unreactive Pd/Al2O3 catalyst. Surface analysis techniques demonstrate the NHC being coordinated to the palladium particles and affecting their electronic properties. Ab initio calculations provide further insight into the electronic effect of the coordination with the NHC injecting electron density into the metal nanocluster thus lowering the barrier for bromobenzene activation. By this NHC modification, the catalyst could be successfully applied in the Buchwald-Hartwig amination of aryl chlorides, bromides, and iodides. Various heterogeneity tests could additionally show that the reaction proceeds via a heterogeneous active species.
- Ernst, Johannes B.,Schwermann, Christian,Yokota, Gen-Ichi,Tada, Mizuki,Muratsugu, Satoshi,Doltsinis, Nikos L.,Glorius, Frank
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supporting information
p. 9144 - 9147
(2017/07/22)
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- Flexible Steric Bulky Bis(Imino)acenaphthene (BIAN)-Supported N-Heterocyclic Carbene Palladium Precatalysts: Catalytic Application in Buchwald-Hartwig Amination in Air
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To achieve efficient palladium-catalyzed cross-coupling reaction under mild reaction conditions with the flexible steric bulk strategy, a series of Pd-PEPPSI (PEPPSI: pyridine-enhanced precatalyst preparation, stabilization, and initiation) complexes C1-C6 were synthesized and characterized, in which unsymmetric flexible steric bulk was introduced on the N-aryl of ancenaphthyl skeleton. These well-defined palladium complexes were found to be excellent precatalysts for Buchwald-Hartwig amination of aryl chlorides with amines in air. The electronic effect of the Pd-PEPPSI complexes and the effect of ancillary pyridine ligands were evaluated, among which complex C3 exhibited the most efficiency. It was demonstrated that the cross-coupling products were obtained in excellent yields in the presence of 0.5-0.1 mol % palladium loading. A wide range of aryl- and heteroaryl chlorides as well as various amines were compatible. The oxidative addition of aryl chlorides is revealed to be the rate-determining step in the catalytic cycle. The catalytic activity can be enhanced by introducing electron-donating groups to the Pd-PEPPSI complexes. This type of Pd-PEPPSI precatalyst showed the most efficiency reported to date for the challenging C-N cross-coupling reactions requiring no anhydrous and inert atmosphere protections, suggesting flexible steric bulk as a promising catalyst design strategy.
- Lan, Xiao-Bing,Li, Yinwu,Li, Yan-Fang,Shen, Dong-Sheng,Ke, Zhuofeng,Liu, Feng-Shou
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p. 2914 - 2925
(2017/03/23)
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- Application of a 2-aryl indenylphosphine ligand in the Buchwald-Hartwig cross-coupling reactions of aryl and heteroaryl chlorides under the solvent-free and aqueous conditions
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An efficient solvent-free protocol for the Buchwald-Hartwig cross-coupling reaction of aryl and heteroaryl chlorides with primary and secondary amines using the Pd(dba)2/ligand 1 catalytic system has been developed. Notably, the catalytic system also efficiently catalyzed the reaction under aqueous conditions.
- Liu, Yan,Yuan, Jia,Wang, Zi-Fei,Zeng, Si-Hao,Gao, Meng-Yue,Ruan, Mei-Lin,Chen, Jian,Yu, Guang-Ao
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supporting information
p. 5805 - 5810
(2017/07/22)
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- Highly Chemoselective Iridium Photoredox and Nickel Catalysis for the Cross-Coupling of Primary Aryl Amines with Aryl Halides
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A visible-light-promoted iridium photoredox and nickel dual-catalyzed cross-coupling procedure for the formation C?N bonds has been developed. With this method, various aryl amines were chemoselectively cross-coupled with electronically and sterically diverse aryl iodides and bromides to forge the corresponding C?N bonds, which are of high interest to the pharmaceutical industries. Aryl iodides were found to be a more efficient electrophilic coupling partner. The coupling reactions were carried out at room temperature without the rigorous exclusion of molecular oxygen, thus making this newly developed Ir-photoredox/Ni dual-catalyzed procedure very mild and operationally simple.
- Oderinde, Martins S.,Jones, Natalie H.,Juneau, Antoine,Frenette, Mathieu,Aquila, Brian,Tentarelli, Sharon,Robbins, Daniel W.,Johannes, Jeffrey W.
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supporting information
p. 13219 - 13223
(2016/10/30)
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- A coordination driven supramolecular Pd2L4self-assembly as heterogeneous catalyst for Buchwald-Hartwig amination reaction
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A Pd2L4type supramolecular coordination driven self assembly was constructed using a dipodal pyridyl terminal ligand L [L = N2,N6-dimethyl-N2,N6-bis((pyridin-4-yl)methyl)naphthalene-2,6-dicarboxamide] and palladium nitrate. The self-assembly was fully characterized by 1D and 2D NMR, ESI-MS, IR, TGA, HR-TEM and elemental analysis. The geometry optimization was performed using the Hartree-Fock method. The assembly acts as an efficient, reusable, heterogeneous catalyst for Buchwald-Hartwig amination reaction in toluene under phosphine free condition and aerobic medium.
- Pradhan, Subhashis,Bhattacharyya, Arya,John, Rohith P.
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p. 1532 - 1536
(2017/03/01)
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- Palladium-Catalyzed N-Arylation of Amines and Amides with Aryltrimethylgermanes
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Described herein is a novel palladium-catalyzed C-N bond-formation reaction employing aryltrimethylgermanes as the new arylating reagents. Primary/secondary amines or even amides could be smoothly arylated to provide the corresponding N-arylation products in moderate to excellent yields.
- Zhang, Qiang,Liu, Cunfang,Shi, Juan,Xu, Qiong,Jin, Lingxia,Zhao, Chaibin,Zhang, Tianlei
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supporting information
p. 1945 - 1948
(2016/08/09)
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- The solid copper-mediated C-N cross-coupling of phenylboronic acids under continuous flow conditions
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We have developed two general methods for the C-N cross-coupling of phenylboronic acids with amines using solid copper flow reactors, in combination with an oxidant. We have developed one method for a C-N arylation reaction which employs a solid copper coil reactor, in combination with tert-butyl peroxybenzoate, to give products in moderate isolated yields. We have also developed a general method for the C-N cross coupling of phenylboronic acids using a column packed with solid copper powder, in combination with acetic acid and TEMPO, to give products in isolated yields in excess of 75+%. We have also applied our general copper powder method to generate a library of products which highlights the utility of solid copper flow reactors for C-N cross coupling reactions, generating 16 examples in good yields. Mechanistic implications and future directions are also discussed.
- Bao, Jennifer,Tranmer, Geoffrey K.
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p. 654 - 657
(2016/01/26)
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- Solvent-Free Buchwald-Hartwig (Hetero)arylation of Anilines, Diarylamines, and Dialkylamines Mediated by Expanded-Ring N-Heterocyclic Carbene Palladium Complexes
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A highly efficient solvent-free protocol for the Buchwald-Hartwig (hetero)arylation of anilines, diarylamines, and dialkylamines mediated by the expanded-ring N-heterocyclic carbene palladium complex (THP-Dipp)Pd(cinn)Cl [THP-Dipp = 1,3-bis(2,6-diisopropylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene; cinn = cinnamyl, 3-phenylallyl] was developed. The catalytic protocol was efficient for the coupling of amines and (hetero)aryl chlorides and bromides bearing donor, acceptor, and bulky substituents.
- Topchiy, Maxim A.,Dzhevakov, Pavel B.,Rubina, Margarita S.,Morozov, Oleg S.,Asachenko, Andrey F.,Nechaev, Mikhail S.
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supporting information
p. 1908 - 1914
(2016/04/20)
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- Water-soluble palladacycles containing hydroxymethyl groups: Synthesis, crystal structures and use as catalysts for amination and Suzuki coupling of reactions
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Two water-soluble monophosphine [PPh3 and 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl(Sphos)]-palladacycles containing hydroxymethyl groups 2-3 were prepared by cyclopalladation and chloride bridge-splitting reactions. The complexes were characterized by elemental analysis, ESI-MS and NMR. In addition, single-crystal X-ray analysis reveals that they have one-dimensional lamellar structures involving intermolecular hydrogen bonds and π-π interactions. The use of these palladacycles as catalysts for amination and Suzuki coupling of aryl chlorides in water was investigated. Complex 3 was found to be very efficient for these coupling reactions. Additionally, it was also successfully used in Suzuki coupling of (hydroxymethyl)phenylboronic acid for the synthesis of substituted 2-N-heterocyclic biarylmethanols.
- Han, Xin,Li, Hong-Mei,Xu, Chen,Xiao, Zhi-Qiang,Wang, Zhi-Qiang,Fu, Wei-Jun,Hao, Xin-Qi,Song, Mao-Ping
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p. 403 - 411
(2016/04/19)
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- Earth abundant metal complexes of donor functionalised N-heterocyclic carbene ligands: synthesis, characterisation and application as amination catalysts
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Six new imidazolium salts of the form 3-R-1-picolylimidazolium bromide (1a: R = 4-nitrophenyl, 1b: R = 4-acetylphenyl, 1c: R = 4-cyanophenyl, 1d: R = allyl, 1e: R = butenyl, 1f: R = pentenyl) were synthesised and isolated in high yields. The corresponding Ag-NHC intermediate complexes 2a, 2d, and 2e were transmetalated to yield [M(NHC)2Cl2 M = Co, Ni] complexes in good to excellent yields. The Co-NHC (3a, 3d, 3e) and Ni-NHC (3a′, 3d′, 3e′) complexes were relatively stable in air, insoluble in chlorinated solvents but very soluble in methanol and DMSO. Poorly resolved NMR spectra and magnetic susceptibility values of 2.53 and 2.73 μB for 3d and 3e respectively suggest both to be paramagnetic cobalt complexes. All the imidazolium salts, isolated Ag-NHC complexes and the corresponding Co and Ni-NHC complexes were characterised by spectroscopic and analytical techniques. The complexes were found to be active at low catalyst loading (1 mol%) for the C-N coupling of aniline with phenyl bromide under mild reaction conditions. In addition, the in situ generated catalyst obtained from a mixture of NiCl2/1a (1:2 molar ratio) initiated the C-N coupling of several aryl amines with substituted aryl bromides bearing a wide variety of functional groups. Good to excellent yields of the desired diaryl amine products were obtained. The yields are comparable to data obtained with palladium catalysts or to data obtained under harsher temperature conditions of Cu mediated Ullman reactions.
- Ibrahim, Halliru,Bala, Muhammad Dabai
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p. 6986 - 6997
(2016/08/09)
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- Application of nanoparticle mediated N-arylation of amines for the synthesis of pharmaceutical entities using vit-E analogues as amphiphiles in water
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The first CuI-nanoparticle catalyzed inter and intramolecular N-arylation of amines using vitamin E analogues (TPGS) as amphipiles has been developed in water. Application of this transition metal-amphiphile C-N bond formation methodology is further extended for the synthesis of substituted indoles, bioactive natural product tryptanthrin and intermediates of pharmaceutical entities such as imatinib, nilotinib, selective D3 agonist/antagonist ligands, and oxacarbazepine. This journal is
- Kumar, Atul,Bishnoi, Ajay Kumar
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p. 20516 - 20520
(2015/03/30)
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- N-arylation of amines: C-N coupling of amines with arylboronic acids using Fe3O4 magnetic nanoparticles-supported EDTA-Cu(ii) complex in water
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Fe3O4 magnetic nanoparticles-supported EDTA-copper(ii) complex (Fe3O4-EDTA-Cu(ii)) has been prepared and characterized by TEM, SEM, XRD, VSM, TGA, and FT-IR spectrometers. The catalyst was applied for the C-N coupling of arylboronic acids with amines for the preparation of N-aryl compounds. Recovery tests confirm that the catalyst can be easily recovered and reused up to eight times without significant loss of its catalytic activity.
- Mostafalu, Ramin,Kaboudin, Babak,Kazemi, Foad,Yokomatsu, Tsutomu
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p. 49273 - 49279
(2014/12/10)
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- A catalyst system, copper/ N -methoxy-1 H -pyrrole-2-carboxamide, for the synthesis of phenothiazines in poly(ethylene glycol)
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A copper/N-methoxy-1H-pyrrole-2-carboxamide catalyst system has been established for the preparation of phenothiazines in good yields by two routes, starting from 2-iodoanilines and 2-bromobenzenethiol and from aryl ortho-dihalides and o-aminobenzenethiols, by conducting the reaction at 90 °C in poly(ethylene glycol)-100 (PEG-100). In addition, the catalyst system was useful for promoting direct arylation of various aryl amines, aliphatic amines, and aqueous ammonia. The simple experimental operation, low loading of catalyst system together with the use of green solvent, makes it attractive for the versatile syntheses of phenothiazines and various amines.
- Huang, Manna,Hou, Jianying,Yang, Ruiqiao,Zhang, Liting,Zhu, Xinhai,Wan, Yiqian
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supporting information
p. 3356 - 3364
(2015/02/02)
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- Direct amination of phenols under metal-free conditions
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Herein, we disclose the metal-free synthesis of arylamines via the direct amination of phenols using aminating reagents. This reaction procedure uses easy accessible aminating reagents and provides a versatile synthetic route to a broad range of arylamines with various functionalities in good to excellent yield. By using a two-step route of amination and oxidative coupling reaction, we synthesized three naturally occurring carbazole alkaloids: murrayafoline A, mukonine, and clausenine from two commercially available phenols. Georg Thieme Verlag Stuttgart · New York.
- Yu, Jianzhong,Wang, Yongtao,Zhang, Peizhi,Wu, Jun
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supporting information
p. 1448 - 1454
(2013/07/26)
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- Ligand-free C-N bond formation in aqueous medium using a reusable Cu-Mn bimetallic catalyst
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A general ligand-free protocol has been described for the recyclable and reusable Cu-Mn catalyzed C-N bond forming cross coupling reaction of arylboronic acids with various amines to form N-arylated amine products in aqueous medium affording excellent yields under ambient conditions, in 3-4 h.
- Sawant, Sanghapal D.,Srinivas, Mahesuni,Aravinda Kumar,Lakshma Reddy,Singh, Parvinder Pal,Singh, Baldev,Sharma, Amit Kumar,Sharma,Vishwakarma, Ram A.
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p. 5351 - 5354
(2013/09/12)
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- A recyclable Cu-catalyzed C-N coupling reaction in water and its application to synthesis of imidazo[1,2-a]quinoxaline
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Polystyrene-supported pyrrole-2-carbohydrazide (PSP) was synthesized and combined with CuI to make up a recyclable heterogeneous catalytic system for Ullmann-type C-N coupling reaction in water. In which, a variety of functionalized aryl halides animated efficiently with anilines, benzylamine, aliphatic amines, and imidazole. its preliminary application resulted in a more practical synthesis of imidazo[1,2-a]quinoxaline.
- Huang, Liye,Yu, Ruina,Zhu, Xinhai,Wan, Yiqian
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supporting information
p. 8974 - 8977
(2013/09/23)
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- Cooperatively assisted N-arylation using organic ionic base-Br?nsted acid combination under controlled microwave heating
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A new synthetic strategy is developed for the construction of C-N bond through the assistance of Br?nsted acid/[DBU][HOAc] without adding any metal catalyst. This is the first efficient SNAr methodology utilizing fluoro, chloro, bromo, and iodoarenes as coupling partners, which offers excellent yield up to 94% within a very short time.
- Singh, Rahul,Allam, Bharat Kumar,Raghuvanshi, Dushyant Singh,Singh, Krishna Nand
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p. 1038 - 1042
(2013/02/23)
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- Nickel-catalyzed synthesis of diarylamines via oxidatively induced C-N bond formation at room temperature
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A nickel-catalyzed oxidative coupling of zinc amides with organomagnesium compounds selectively produces diarylamines under mild reaction conditions, with tolerance for chloride, bromide, hydroxyl, ester, and ketone groups. A diamine is bis-monoarylated. A bromoaniline undergoes N-arylation followed by Kumada-Tamao-Corriu coupling in one pot. The reaction may proceed via oxidatively induced reductive elimination of a nickel species.
- Ilies, Laurean,Matsubara, Tatsuaki,Nakamura, Eiichi
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supporting information
p. 5570 - 5573,4
(2012/12/12)
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- Nickel-mediated N-arylation with arylboronic acids: An avenue to Chan-Lam coupling
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An efficient use of NiCl2·6H2O, for the cross-coupling of arylboronic acids with various N-nucleophiles, has been demonstrated. The method is practical and offers an alternative to the corresponding Cu-mediated Chan-Lam process for the construction of the C-N bond.
- Raghuvanshi, Dushyant Singh,Gupta, Amit Kumar,Singh, Krishna Nand
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supporting information
p. 4326 - 4329
(2012/10/29)
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- N-Heterocyclic carbene adducts of cyclopalladated ferrocenylpyridine: Synthesis, structural characterization and reusable catalytic system for Suzuki and amination of aryl chlorides in poly(ethylene glycol-400)
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Two air-stable carbene adducts of cyclopalladated ferrocenylpyridine 1-2 have been synthesized and characterized by elemental analysis, IR, ESI-MS, 1H and 13C NMR. Additionally, their detailed structures have been determined by singl
- Xu, Chen,Li, Hong-Mei,Liu, Hu,Zhang, Zhi-Qiang,Wang, Zhi-Qiang,Fu, Wei-Jun,Zhang, Yu-Qing
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experimental part
p. 22 - 26
(2012/06/15)
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- Efficient palladium-catalyzed amination of aryl chlorides using di(dicyclohexylamino)phenylphosphine as a PN2 ligand
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The palladium-catalyzed amination of a variety of aryl chlorides has been accomplished by using di(dicyclohexylamino)phenylphosphine (1) as a bulky electron-rich monoaryl phosphine ligand. The optimized condition for the palladium-catalyzed amination of aryl chloride is the followings: aniline (3.0 mmol, 1.0 equiv), chlorobenzene (3.15 mmol, 1.05 equiv), ligand 1 (1 mol %, 0.03 mmol), KOtBu (4.5 mmol, 1.5 equiv), Pd2(dba)3 (1 mol %, 0.03 mmol), and toluene as solvent at reflux temperature. We report on couplings of various amines or chloroamines with chlorobenzenes and heteroaryl chloride.
- Kim, Bo Ram,Cho, Su-Dong,Kim, Eun Jung,Lee, In-Hye,Sung, Gi Hyeon,Kim, Jeum-Jong,Lee, Sang-Gyeong,Yoon, Yong-Jin
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experimental part
p. 287 - 293
(2012/01/05)
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