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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
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
p. 22278 - 22286
(2021/07/02)

Synergistic effect of copper nanocrystals-nanoparticles incorporated in a porous organic polymer for the Ullmann C-O coupling r–eaction
A quinoxaline-based porous organic polymer (Q-POP) as a mesoporous organic copolymer was developed as a new platform for the immobilization of CuNPs and copper nanocrystals. The prepared materials were characterized by FT-IR, XRD, N2 adsorption-desorption isotherms, ICP, TGA, SEM, HR-TEM, EDX, and single-crystal X-ray crystallography. The obtained catalyst presented extraordinary catalytic activity towards Ullmann C–O coupling reactions with high surface area, hierarchical porosity, and excellent thermal and chemical stability. Due to its high porosity, and synergistic effect of copper nanocrystals incorporated in the polymer composite, the as-synthesized catalyst was successfully utilized for the Ullmann C–O coupling reaction of phenols and different aryl halides to prepare various diaryl ether derivatives. All types of aryl halides (except aryl fluorides) were screened in the Ullmann C–O coupling reaction with phenols to produce diaryl ethers in good to excellent yields (70–97 %), and it was found 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
(2021/02/22)

Magnetization of graphene oxide nanosheets using nickel magnetic nanoparticles as a novel support for the fabrication of copper as a practical, selective, and reusable nanocatalyst in C-C and C-O coupling reactions
Catalyst species are an important class of materials in chemistry, industry, medicine, and biotechnology. Moreover, waste recycling is an important process in green chemistry and is economically efficient. Herein, magnetic graphene oxide was synthesized using nickel magnetic nanoparticles and further applied as a novel support for the fabrication of a copper catalyst. The catalytic activity of supported copper on magnetic graphene oxide (Cu-ninhydrin@GO-Ni MNPs) was investigated as a selective, practical, and reusable nanocatalyst in the synthesis of diaryl ethers and biphenyls. Some of the obtained products were identified by NMR spectroscopy. This nanocatalyst has been characterized by atomic absorption spectroscopy (AAS), scanning electron microscopy (SEM), wavelength dispersive X-ray spectroscopy (WDX), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), and vibrating sample magnetometer (VSM) techniques. The results obtained from SEM shown that this catalyst has a nanosheet structure. Also, XRD and FT-IR analysis show that the structure of graphene oxide and nickel magnetic nanoparticles is stable during the modification of the nanoparticles and synthesis of the catalyst. The VSM curve of the catalyst shows that this catalyst can be recovered using an external magnet; therefore, it can be reused several times without a significant loss of its catalytic efficiency. The heterogeneity and stability of this nanocatalyst during organic reactions was confirmed by the hot filtration test and AAS technique.
Hajjami, Maryam,Moradi, Parisa
p. 25867 - 25879
(2021/08/09)

Oxidative Photochlorination of Electron-Rich Arenes via in situ Bromination
Electron-rich arenes are oxidatively photochlorinated in the presence of catalytic amounts of bromide ions, visible light, and 4CzIPN as organic photoredox catalyst. The substrates are brominated in situ in a first photoredox-catalyzed oxidation step, followed by a photocatalyzed ipso-chlorination, yielding the target compounds in high ortho/para regioselectivity. Dioxygen serves as a green and convenient terminal oxidant. The use of aqueous hydrochloric acid as the chloride source reduces the amount of saline by-products.
Düsel, Simon Josef Siegfried,K?nig, Burkhard
supporting information
p. 1491 - 1495
(2019/04/30)

CoII Immobilized on Aminated Magnetic-Based Metal–Organic Framework: An Efficient Heterogeneous Nanostructured Catalyst for the C–O Cross-Coupling Reaction in Solvent-Free Conditions
Abstract: In this paper, we report the synthesis of Fe3O4?AMCA-MIL53(Al)-NH2-CoII NPs based on the metal–organic framework structures as a magnetically separable and environmentally friendly heterogeneous nanocatalyst. The prepared nanostructured catalyst efficiently promotes the C–O cross-coupling reaction in solvent-free conditions without the need for using toxic solvents and/or expensive palladium catalyst. Graphic Abstract: [Figure not available: see fulltext.].
Mohammadinezhad, Arezou,Akhlaghinia, Batool
p. 332 - 352
(2020/01/11)

Trimethoxyphenyl (TMP) as a Useful Auxiliary for in situ Formation and Reaction of Aryl(TMP)iodonium Salts: Synthesis of Diaryl Ethers
Herein, we describe a synthetic approach for arylation that exploits the in situ formation and reaction of an unsymmetrical diaryliodonium salt. In this way, aryl iodides are used as reagents in a metal-free reaction with phenols, and a trimethoxyphenyl (TMP) group is used as a “dummy” group to facilitate transfer of a wide range of aryl moieties. The scope of aryl electrophiles and phenol nucleophiles is broad (>30 examples) and the yields are high (52–95%, 80% avg.). One-pot coupling reactions avoid the synthesis of diaryliodonium salts and provide opportunities for sequential reactions and novel chemoselectivity. (Figure presented.).
Gallagher, Rory T.,Basu, Souradeep,Stuart, David R.
p. 320 - 325
(2019/12/11)

Diaza crown-type macromocycle (kryptofix 22) functionalised carbon nanotube for efficient Ni2+ loading; A unique catalyst for cross-coupling reactions
Raising the capability of supporting and suppressing the leaching possibility to a very insignificant level has still remained challenging for some class of transition metals, i.e. Ni2+. Here we present the covalent functionalisation of macrocyclic ligand, 4,13-diaza-18-crown-6 (kryptofix 22), on the surface of carbon nanotube (CNT), leading to a unique adsorptive capability for supporting Ni2+. This material was incorporated as a promising catalyst in coupling reactions including C[sbnd]C, CN, and CO[sbnd][sbnd] cross-coupling reactions. We demonstrate that the kryptofix 22 functionalisation on the surface of CNT has a key role in the enhancement of the adsorption capability Ni2+ and subsequent catalytic activity. We further prove that this ligand causes a significant boost in the recyclability of the reactions due to the extremely trivial Ni2+ leaching from the CNT's surface during the reactions.
Aalinejad, Michael,Doustkhah, Esmail,Pesyan, Nader Noroozi
(2020/07/13)

Palladium complexes of chalcogenoethanamine (S/Se) bidentate ligands: Applications in catalytic arylation of C[sbnd]H and O[sbnd]H bonds
This report describes the syntheses of N,E (E = S, Se) coordinated bidentate palladium complexes, by the reaction of N-(2-bromobenzyl)-2-(phenylthio/selanyl)ethanamine (3, 4) with [PdCl2(CH3CN)2]. The new ligands and palladium complexes were characterized by techniques like 1H, 13C{1H} NMR, IR, and elemental analysis. The coordination modes of ligand with palladium precursor in complexes 5 and 6 were authenticated by single crystal X-ray diffraction. The complexes possess distorted square planar geometry around palladium center. Thermally robust and air stable complexes 5 and 6 were used as catalyst for regioselective arylation of imidazole and O-arylation of phenol. In case of regioselective arylation of imidazole, the reaction proceeds smoothly under mild reaction conditions, only 2.0 mol% of catalyst loading is required to achieve high yield (76–92%). This protocol is applicable to a broad substrate scope showing excellent tolerance towards different functional groups. Whereas for O-arylation of phenol also only 2.0 mol% catalyst loading is sufficient to give good yield (71–92%) with excellent tolerance towards a broad range of functional groups. Among sulfur and selenium coordinated ligands, selenium ligand coordinated complex, was found to outperform the catalytic reactions in both cases as compare to sulfur ligand. The mercury and triphenylphosphine poisoning tests suggest homogeneous nature of catalysis.
Bhatt, Ramprasad,Bhuvanesh, Nattamai,Himanshi,Joshi, Hemant,Sharma, Alpesh K.
(2020/05/18)

Magnetically recyclable nano copper/chitosan in O-arylation of phenols with aryl halides
Interaction of chitosan (CS) with Fe3O4, followed by embedding Cu nanoparticles (NPs) on the magnetic surface through adsorption of Cu2+, and its reduction to Cuo via NaBH4, offers a reusable efficient catalyst (Fe3O4/CS-Cu NPs) that is employed in cross-coupling reactions of aryl halides with phenols, which affords the corresponding diaryl ethers, with good to excellent yields. The catalyst is completely recoverable from the reaction mixture by using an external magnet. It can be reused four times, without significant loss in its catalytic activity.
Mousavi Mashhadi, Seyed Ali,Kassaee, Mohamad Z.,Eidi, Esmaiel
(2019/07/04)

Cu(I)-PNF, an organic-based nanocatalyst, catalyzed C-O and C-S cross-coupling reactions
Peptide nanofiber has been prepared via a self-assembly protocol and decorated with Cu(I) to prepare a nanostructural catalyst. The catalytic activity of this prepared nanomaterial (Cu(I)-PNF) was examined in C-O and C-S cross-coupling reactions. Compared with conventional copper-ligand catalytic systems, CuNP-PNF has unique advantages such as water solubility, high efficiency, and low cost, which makes it a highly efficient and beneficial catalyst to reuse in cross-coupling reactions.
Taherinia, Zahra,Ghorbani-Choghamarani, Arash
p. 46 - 52
(2019/01/10)

Flow hydrodediazoniation of aromatic heterocycles
Continuous flow processing was applied for the rapid replacement of an aromatic amino group with a hydride. The approach was applied to a range of aromatic heterocycles, confirming the wide scope and substituent-tolerance of the processes. Flow equipment was utilized and the process optimised to overcome the problematically-unstable intermediates that have restricted yields in previous studies relying on batch procedures. Various common organic solvents were investigated as potential hydride sources. The approach has allowed key structures, such as amino-pyrazoles and aminopyridines, to be deaminated in good yield using a purely organic-soluble system.
R?der, Liesa,Nicholls, Alexander J.,Baxendale, Ian R.
(2019/06/05)

URJC-1-MOF as New Heterogeneous Recyclable Catalyst for C-Heteroatom Coupling Reactions
Guillermo Calleja and co-workers from @urjc describe URJC-1-MOF as a new heterogeneous recyclable catalyst for c-heteroatom coupling reactions. The capacity of copper-based URJC-1-MOF as a MOF catalyst in cross-coupling reactions has been evaluated, focusing on the Chan-Lam-Evans arylation-type reactions on amines and alcohols without extra additives or ligands. The extraordinary chemical and structural stability of URJC-1-MOF and its good specific surface, make this material a promising alternative to homogeneous Cu (II) catalysts for cross-coupling reactions. URJC-1-MOF showed a remarkable catalytic activity for cross-coupling C?N and C?O reactions, higher than other heterogeneous and homogeneous copper-based catalyst, such as CuO, HKUST-1, Cu?MOF-74, Cu(OAc)2 and CuSO4?5H2O. Moreover, its easy recovery by simple filtration and reusability in successive runs without any loss of activity and stability, demonstrates the potential of URJC-1-MOF as an alternative catalyst for this kind of reactions in different chemical media of industrial interest.
Mu?oz, Antonio,Leo, Pedro,Orcajo, Gisela,Martínez, Fernando,Calleja, Guillermo
p. 3376 - 3380
(2019/07/04)

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
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
p. 6408 - 6422
(2018/05/31)

CERAMIDE GALACTOSYLTRANSFERASE INHIBITORS FOR THE TREATMENT OF DISEASE
Described herein are compounds, methods of making such compounds, pharmaceutical compositions and medicaments containing such compounds, and methods of using such compounds to treat or prevent diseases or disorders associated with the enzyme ceramide galactosyltransferase (CGT), such as, for example, lysosomal storage diseases. Examples of lysosomal storage diseases include, for example, Krabbe disease and Metachromatic Leukodystrophy.
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(2018/07/29)

Synthesis and characterization of MCM-41-Biurea-Pd as a heterogeneous nanocatalyst and using its catalytic efficacy in C–C, C–N and C–O coupling reactions
MCM-41-Biurea-Pd is introduced as a new, heterogeneous and reusable catalyst for C–C and C–heteroatom bond formation between various aryl halides, phenols and amines, in the presence of Ph3SnCl (Stille reaction) in PEG-400 as a green solvent at room temperature. The structure of the functionalized MCM-41 was analysed using various techniques.
Batmani, Hana,Noroozi Pesyan, Nader,Havasi, Forugh
(2018/07/31)

Zirconium oxide complex anchored on boehmite nanoparticles as highly reusable organometallic catalyst for C–S and C–O coupling reactions
Boehmite nanoparticles were prepared by a simple and inexpensive procedure in water using commercially available materials without inert atmosphere. Then, the surface of the boehmite nanoparticles was modified using 3-mercaptopropyltrimethoxysilane and subsequently zirconium oxide was supported on the modified surface. Zirconium oxide supported on boehmite nanoparticles (Pr.S-ZrO@boehmite) was characterized using scanning electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis and inductively coupled plasma technique. The catalytic application of Pr.S-ZrO@boehmite was studied in C–O and C–S coupling reactions for synthesis of valuable compounds such as ether and sulfide derivatives. All products were obtained in good to excellent yields and the catalyst could be recovered and reused several times without significant loss of catalytic efficiency. Furthermore, zirconium oxide is rarely used as catalyst for cross-coupling reactions.
Ghorbani-Choghamarani, Arash,Seydyosefi, Zeinab,Tahmasbi, Bahman
(2018/07/31)

Cu2O/SiC as efficient catalyst for Ullmann coupling of phenols with aryl halides
A Cu2O/SiC heterogeneous catalyst was prepared via a two-step liquid-phase method using diethylene glycol as both the solvent and the reducing agent. The catalyst was characterized using X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and H2 temperature-programmed reduction. All the results indicate that Cu is present on the SiC support primarily as Cu2O. The SEM and TEM results show that cubic Cu2O nanoparticles are uniformly dispersed on the β-SiC surface. The reaction conditions, namely the temperature, reaction time, and amounts of base and catalyst used, for the Ullmann-type C–O cross-coupling reaction were optimized. A model reaction was performed using iodobenzene (14.0 mmol) and phenol (14.0 mmol) with Cu2O/SiC (5 wt% Cu) as the catalyst, Cs2CO3 (1.0 equiv.) as the base, and tetrahydrofuran as the solvent at 150 °C for 3 h; a yield of 97% was obtained and the turnover frequency (TOF) was 1136 h?1. The Cu2O/SiC catalyst has a broad substrate scope and can be used in Ullmann-type C–O cross-coupling reactions of aryl halides and phenols bearing a variety of different substituents. The catalyst also showed high activity in the Ullmann-type C–S cross-coupling of thiophenol with iodobenzene and substituted iodobenzenes; a TOF of 1186 h?1 was achieved. The recyclability of the Cu2O/SiC catalyst in the O-arylation of phenol with iodobenzene was investigated under the optimum conditions. The yield decreased from 97% to 64% after five cycles. The main reason for the decrease in the catalyst activity is loss of the active component, i.e., Cu2O.
Wang, Yibing,Guo, Xiaoning,Lü, Manqian,Zhai, Zhaoyang,Wang, Yingyong,Guo, Xiangyun
p. 658 - 664
(2017/04/24)

A green approach for arylation of phenols using iron catalysis in water under aerobic conditions
The first efficient iron-catalyzed coupling of aryl iodides with phenols was developed exclusively with water as solvent. The reaction is performed with low cost and readily available FeCl3·6H2O and DMEDA catalytic system providing diaryl ethers in good to excellent yields. The effectiveness of this reaction was further revealed by compatibility with a wide range of functional groups. Moreover, the procedure is rendered simple as this transformation is carried out in the presence of air. Thus, the protocol represents a facile, economical and eco-friendly procedure to access diaryl ethers.
Sindhu, Kallikkakam S.,Ujwaldev, Sankuviruthiyil M.,Keerthi Krishnan,Anilkumar, Gopinathan
p. 146 - 150
(2017/03/17)

Ullmann Reaction Catalyzed by Heterogeneous Mesoporous Copper/Manganese Oxide: A Kinetic and Mechanistic Analysis
A heterogeneous copper oxide supported on mesoporous manganese oxide (meso Cu/MnOx) was explored for Ullmann-type cross-coupling reactions. An inverse micelle-templated evaporation-induced self-assembly method with in situ addition of copper was adopted to synthesize the mesoporous catalyst. Broad substrate scope and excellent functional group tolerability in C-O, C-N, and C-S bond formation reactions were observed using the optimized reaction conditions. The catalytic protocol was ligand free, and the catalyst was reusable without any significant loss of activity. The kinetic and Hammett analyses provided evidence for oxidative addition to a Cu(I) reaction center followed by nucleophilic addition and reductive elimination at the active copper oxide surface. Rate acceleration was observed for aryl halides with electron-withdrawing groups. The Hammett analysis determined ρ = +1.0, indicative of an oxidative addition, whereas the electronic effect in the phenol ring (ρ = -2.9) was indicative of coordination to a metal ion. Theoretically, the oxidative addition of the aryl halides is assisted by the ligand environment of the copper center. Relevant mechanistic implications are discussed on the basis of the experimental and computational results.
Mullick, Kankana,Biswas, Sourav,Kim, Chiho,Ramprasad, Ramamurthy,Angeles-Boza, Alfredo M.,Suib, Steven L.
supporting information
p. 10290 - 10297
(2017/09/12)

Pd-Catalyzed Decarbonylative Cross-Couplings of Aroyl Chlorides
This report describes a method for Pd-catalyzed decarbonylative cross-coupling that enables the conversion of carboxylic acid derivatives to biaryls, aryl amines, aryl ethers, aryl sulfides, aryl boronate esters, and trifluoromethylated arenes. The success of this transformation leverages the Pd0/Brettphos-catalyzed decarbonylative chlorination of aroyl chlorides, which can then participate in diverse cross-coupling reactions in situ using the same Pd catalyst.
Malapit, Christian A.,Ichiishi, Naoko,Sanford, Melanie S.
supporting information
p. 4142 - 4145
(2017/08/15)

Palladium-on-Carbon-Catalyzed Coupling of Nitroarenes with Phenol: Biaryl Ether Synthesis and Evidence of an Oxidative-Addition-Promoted Mechanism
Nucleophilic substitution in nitroarenes to form biaryl ethers is of fundamental importance in organic synthesis. Under non-catalytic conditions, this can occur if highly activated nitroarenes are used or if the nucleophile is activated by a strong stoichiometric base. We established a new method involving the use of a ligand-free palladium-on-carbon (Pd/C) catalyst for the cross-coupling of activated nitroarenes with relatively non-nucleophilic phenol derivatives, including naphthol, in the absence of harsh bases. Control experiments, hot filtration, the three-phase test, and inductively coupled plasma atomic emission spectroscopy analysis revealed that the catalysis proceeded through an usual oxidative addition step of the nitroarene to Pd/C, which resulted in the release of active palladium particles having extremely high catalytic activity. DFT calculations revealed the origin of the selectivity of the activated nitroarenes.
Begum, Tahshina,Mondal, Manoj,Borpuzari, Manash Protim,Kar, Rahul,Gogoi, Pradip K.,Bora, Utpal
supporting information
p. 3244 - 3248
(2017/06/21)

Halogenase-Inspired Oxidative Chlorination Using Flavin Photocatalysis
Chlorine gas or electropositive chlorine reagents are used to prepare chlorinated aromatic compounds, which are found in pharmaceuticals, agrochemicals, and polymers, and serve as synthetic precursors for metal-catalyzed cross-couplings. Nature chlorinates with chloride anions, FAD-dependent halogenases, and O2 as the oxidant. A photocatalytic oxidative chlorination is described based on the organic dye riboflavin tetraacetate mimicking the enzymatic process. The chemical process allows within the suitable arene redox potential window a broader substrate scope compared to the specific activation in the enzymatic binding pocket. Chlorination of arenes with chloride anions: The photochemical analogue of the enzymatic chlorination of Flavin-adenine dinucleotide (FAD)-dependent halogenases is possible in the presence of riboflavin, air, acetic acid, and blue light (see scheme; RFT=riboflavin tetraacetate).
Hering, Thea,Mühldorf, Bernd,Wolf, Robert,K?nig, Burkhard
supporting information
p. 5342 - 5345
(2016/04/26)

Synthesis of copper nanoparticles supported on a microporous covalent triazine polymer: An efficient and reusable catalyst for O-arylation reaction
Copper nanoparticles were supported on a microporous covalent triazine polymer prepared by the Friedel-Crafts reaction (Cu@MCTP-1). The resulting material was characterized by powder X-ray diffraction, thermogravimetric analysis, N2 adsorption-desorption isotherms at 77 K, transmission electron microscopy, X-ray photoelectron spectroscopy, and inductively coupled plasma optical emission spectroscopy, and Cu particles with an average size of 3.0 nm and a BET total surface area of ca. 1002 m2 g-1 were obtained. Cu@MCTP-1 was evaluated as a heterogeneous catalyst for the Ullmann coupling of O-arylation over a series of aryl halides and phenols without employing expensive ligands or inert atmosphere, which produced an excellent yield of the corresponding diaryl ethers. The catalyst could be recovered by simple centrifugation and was reusable at least five times with only a slight decrease in catalytic activity.
Puthiaraj, Pillaiyar,Ahn, Wha-Seung
p. 1701 - 1709
(2016/04/05)

Interface Engineering in Two-Dimensional Heterostructures: Towards an Advanced Catalyst for Ullmann Couplings
The design of advanced catalysts for organic reactions is of profound significance. During such processes, electrophilicity and nucleophilicity play vital roles in the activation of chemical bonds and ultimately speed up organic reactions. Herein, we demonstrate a new way to regulate the electro- and nucleophilicity of catalysts for organic transformations. Interface engineering in two-dimensional heteronanostructures triggered electron transfer across the interface. The catalyst was thus rendered more electropositive, which led to superior performance in Ullmann reactions. In the presence of the engineered 2D Cu2S/MoS2 heteronanostructure, the coupling of iodobenzene and para-chlorophenol gave the desired product in 92 % yield under mild conditions (100 °C). Furthermore, the catalyst exhibited excellent stability as well as high recyclability with a yield of 89 % after five cycles. We propose that interface engineering could be widely employed for the development of new catalysts for organic reactions.
Sun, Xu,Deng, Haitao,Zhu, Wenguang,Yu, Zhi,Wu, Changzheng,Xie, Yi
supporting information
p. 1704 - 1709
(2016/02/03)

Ullmann diaryl ether synthesis catalyzed by copper (I)/pyridine-functionalized silane
Ullmann-type diaryl ether synthesis was performed under mild conditions in DMF/K2CO3using a pyridinefunctionalized silane as a ligand. The productswere obtained in good yields. This method tolerates a variety of functional groups and is effective in the synthesis of hindered diaryl ethers and heteroaryl ethers.
Zhang, Baohua,Shi, Lanxiang,Guo, Ruixia,Liu, Sijie
p. 930 - 932
(2016/07/06)

Photocatalytic activation of N-chloro compounds for the chlorination of arenes
Photoredox catalysis activates N-chloramines and N-chloro-succinimide (NCS) for the electrophilic chlorination of arenes. The photooxidation of the nitrogen atom to a radical cation induces a positive polarization on the chlorine atom, which results in a higher reactivity in electrophilic aromatic chlorination reactions.
Hering, Thea,K?nig, Burkhard
p. 7821 - 7825
(2016/11/16)

Visible-light-mediated synthesis of diaryl ethers from arylboronic acids and diaryliodonium salts
With visible-light irradiation, a simple and metal-free photocatalytic system for the synthesis of diaryl ethers from arylboronic acids and diaryliodonium salts has been developed. The reaction proceeded in high yield for a range of different substrates in the presence of eosin Y under mild reaction conditions.
Liu, Li,Tang, Jiaqi,Qiang, Jian,Li, Jian,He, Mingyang
p. 261 - 264
(2016/07/06)

A method of preparing sodium monoalkyl diphenyl ether disulfonate
A method of preparing sodium monoalkyl diphenyl ether disulfonate is provided. The method includes (1) a step of adding an caustic alkali into melt p-chlorophenol, distilling to remove water produced by a reaction, adding a catalyst, adding dropwise bromobenzene, fully reacting, and adding sulfuric acid for washing after the reaction is finished, allowing the mixture to stand and to be layered, and distilling an upper-layer liquid to obtain a product that is 4-chlorodiphenyl ether, (2) a step of adding magnesium into a solvent, adding dropwise the 4-chlorodiphenyl ether to obtain a 4-chlorodiphenyl ether Grignard reagent solution, adding a catalyst into the Grignard reagent solution, adding dropwise halogeneated n-alkane, and after the reaction is finished, separating by distillation to obtain a product that is monoalkyl diphenyl ether, and (3) a step of adding dropwise a sulfonating agent into the monoalkyl diphenyl ether, adjusting the pH to be 7-10 with sodium hydroxide or sodium carbonate or sodium bicarbonate after the reaction is finished, distilling to remove water, adding a solvent for dissolution, filtering to remove insoluble substances and distilling to obtain a sodium monoalkyl diphenyl ether disulfonate product. The method is high in conversion ratio and can prepare the high-purity sodium monoalkyl diphenyl ether disulfonate product.
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(2016/10/27)

CsF/clinoptilolite: An efficient solid base in SNAr and copper-catalyzed Ullmann reactions
CsF/clinoptilolite was found to be an efficient solid base catalyst for both SNAr and Ullmann ether reactions. A general and efficient one-step procedure was developed for the synthesis of biaryl ethers via direct coupling of electron-deficient aryl halides to phenols using CsF/clinoptilolite. The protocol was also applied to electron-rich aryl halides by addition of a catalytic amount of copper oxide nanoparticles. Both SNAr and Ullmann reactions were rapid and provided good to excellent yields.
Keipour, Hoda,Hosseini, Abolfazl,Afsari, Amir,Oladee, Razieh,Khalilzadeh, Mohammad A.,Ollevier, Thierry
p. 95 - 104
(2016/01/16)

Air-stable palladium(0) phosphine sulfide catalysts for Ullmann-type C-N and C-O coupling reactions
This paper describes an efficient procedure for palladium(0)-catalyzed N-arylation and O-arylation of aryl halides by Ullmann-type cross coupling reaction under mild reaction conditions in a short reaction time. Two phosphine sulphide ligands and their corresponding Pd(0) complexes namely [Pd(p2S2)(dba)] and [Pd(pp3S4)(dba)], were synthesized, where p2S2 is 1,2-bis(diphenylphosphino)ethane disulfide, pp3S4 is tris[2-(diphenylphosphino)ethyl]phosphine tetrasulfide and dba is dibenzylideneacetone. Optimal reaction conditions were determined for the arylation reactions using iodobenzene and benzimidazole by varying temperature, solvent, base and catalyst loading. The cross coupling reactions were carried out taking iodobenzenes/bromobenzenes and a wide variety of substituted aryl amines/phenols/alcohols with different steric and electronic properties to afford the desired N-aryl amines/diaryl ethers/alkyl aryl ethers in good to excellent yield (70-94%).
Majumder, Arpi,Gupta, Ragini,Mandal, Mrinmay,Babu, Madhu,Chakraborty, Debashis
p. 23 - 34
(2015/03/05)

Barberry fruit extract assisted in situ green synthesis of Cu nanoparticles supported on a reduced graphene oxide-Fe3O4 nanocomposite as a magnetically separable and reusable catalyst for the O-arylation of phenols with aryl halides under ligand-free conditions
In situ synthesis of copper nanoparticles (NPs) supported on a reduced graphene oxide (RGO)-Fe3O4 nanocomposite was carried out with barberry fruit extract as a reducing and stabilizing agent. The morphology and structure of the Cu/RGO-Fe3O4 nanocomposite was fully characterized by means of X-ray diffraction (XRD), Fourier transformed infrared (FT-IR) spectroscopy, field emission scanning electron microscopy (FE-SEM), Raman, energy dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM). Cu/RGO-Fe3O4 was a promising catalyst for the O-arylation of phenols with aryl halides under ligand-free conditions. A diverse range of diaryl ethers were obtained in a good to high yield. Furthermore, due to the magnetic separability and high stability of the composite the catalyst could be separated conveniently from the reaction mixtures by an external permanent magnet and recycled multiple times without loss of catalytic activity.
Nasrollahzadeh, Mahmoud,Maham, Mehdi,Rostami-Vartooni, Akbar,Bagherzadeh, Mojtaba,Sajadi, S. Mohammad
p. 64769 - 64780
(2015/08/18)

A highly active and recyclable catalyst for the synthesis of indole and phenyl ether
A new simple catalytic system consisting of copper-aluminium and hydrotalcite (CuAl-HT) has been developed using a facile one-pot method without harm to the environment. The catalyst was characterized using TEM, XRD and XPS. It could be used as an efficient catalyst for the synthesis of both indole and phenyl ether. As expected, the catalyst afforded high catalytic activity for the selective synthesis of indole via intramolecular dehydrogenative N-heterocyclization of 2-(2-aminophenyl)ethanol. Meanwhile, it also exhibited superior catalytic properties for an Ullmann-type coupling reaction to synthesise phenyl ether from iodobenzene and phenol. The CuAl-HT catalyst showed higher activity than conventional catalysts based on copper and could be recycled several times with stable catalytic activity. This procedure has real economic advantages since no expensive materials were used.
Qiao, Bo,Zhang, Le,Li, Rong
p. 93463 - 93469
(2015/11/17)

A counteranion triggered arylation strategy using diaryliodonium fluorides
A mild and transition metal-free counteranion triggered arylation strategy has been developed using diaryliodonium fluorides. The fluoride counteranion within the hypervalent iodonium species displays unusual reactivity that activates a phenolic O-H bond leading to electrophilic O-arylation. A wide range of phenols and diaryliodonium salts are compatible with this transformation under remarkably mild conditions. Furthermore, we pre-empt the wider implications of this strategy by demonstrating the compatibility of the arylation tactic with latent carbon nucleophiles.
Chan,McNally,Toh,Mendoza,Gaunt
p. 1277 - 1281
(2015/02/05)

Anchoring of Pd(ii) complex in functionalized MCM-41 as an efficient and recoverable novel nano catalyst in C-C, C-O and C-N coupling reactions using Ph3SnCl
Anchored palladium(ii) in functionalized MCM-41 mesoporous silica was prepared and used as an efficient, recoverable and thermally stable heterogeneous nano catalyst for C-C, C-O and C-N bond formation in cross-coupling reactions in the presence of Ph3SnCl. MCM-41 was prepared trough hydrothermal synthesis using tetraethyl orthosilicate (Si(OC2H5)4) as silica source and cetyltrimethylammonium bromide (CTAB) as a template. The structure of functionalized MCM-41 was studied by FT-IR, XRD, SEM, TEM, TGA, EDS, ICP and BET techniques.
Ghorbani-Choghamarani, Arash,Nikpour, Farzad,Ghorbani, Farshid,Havasi, Forugh
p. 33212 - 33220
(2015/04/27)

A highly active reusable polymer anchored copper catalyst for C-O, C-N and C-S cross coupling reactions
A new furfural functionalized polymer-amine grafted with copper catalyst has been designed and employed for the N-arylation, O-arylation and S-arylation reactions under an open air condition to afford the corresponding coupled products in good to excellent yields. This solid supported catalyst was characterized by Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), UV-vis spectroscopy and scanning electron microscope (SEM). The developed catalyst can be facilely recovered and reused five times without significant decrease in activity and selectivity. This result confirms that the polymer anchored complex was not leached during the reaction, suggesting the true heterogeneous nature of the catalyst.
Islam, Sk.Manirul,Salam, Noor,Mondal, Paramita,Roy, Anupam Singha,Ghosh, Kajari,Tuhina
p. 7 - 19
(2014/04/03)

Highly active recyclable heterogeneous Pd/ZnO nanoparticle catalyst: Sustainable developments for the C-O and C-N bond cross-coupling reactions of aryl halides under ligand-free conditions
Efficient Pd supported on ZnO nanoparticles for the ligand-free O-arylation and N-arylation of phenols and various N-H heterocycles with aryl chlorides, bromides, and iodides were readily synthesized and characterized. The amount of palladium on ZnO is 9.84 wt% (0.005 g of the catalyst contains 462 × 10-8 mol% of Pd) which was determined by ICP analysis. This nano sized Pd/ZnO with an average particle size of 20-25 nm and specific surface area 40.61 m2 g-1 was used as a new reusable heterogeneous catalyst for the formation of C-O and C-N bonds in organic synthesis. This protocol gives the arylated product in satisfactory yields without any N2 or Ar flow. The catalyst can be recovered and recycled several times without marked loss of activity.
Hosseini-Sarvari, Mona,Razmi, Zahra
p. 44105 - 44116
(2014/12/10)

Copper-catalyzed Ullmann-type synthesis of diaryl ethers assisted by salicylaldimine ligands
A series of salicylaldimine ligands were designed to promote the copper-catalyzed Ullmann cross-coupling reaction. After a screening process, 2-((2-isopropylphenylimino)methyl)phenol was found to serve as a good supporting ligand for this reaction. Employing this Schiff-base ligand as a new supporting ligand, the copper-catalyzed coupling reactions of aryl bromides and aryl iodides with various phenols successfully proceeded in good yields under mild conditions. Various diaryl ethers were obtained with excellent yields in dioxane in the presence of K3PO4 and a catalytic amount of copper(I) salt.
Qian, Cun-Wei,Lv, Wen-Lin,Zong, Qian-Shou,Wang, Mao-Yuan,Fang, Dong
p. 337 - 340
(2014/02/14)

KF/Clinoptilolite, an effective solid base in Ullmann ether synthesis catalyzed by CuO nanoparticles
Employing KF/Clinoptilolite as an efficient base the cross-coupling reactions of various phenols with aryl iodides could be successfully carried out in the presence of copper oxide nanoparticles. The C-O coupling products were obtained in moderate to good yields (62-87%) for a variety of substrates. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2014.
Khalilzadeh, Mohammad A.,Keipour, Hoda,Hosseini, Abolfazl,Zareyee, Daryoush
p. 42 - 45
(2014/01/06)

Chemoselective and ligand-free synthesis of diaryl ethers in aqueous medium using recyclable alumina-supported nickel nanoparticles
An economical and eco-compatible ligand-free protocol for the synthesis of diaryl ethers has been developed using easily accessible alumina-supported nickel nanoparticles as a stable recyclable heterogeneous catalyst in aqueous medium along with a surfactant (SDS) and a mild base (K2CO3). Various sensitive functional groups like allyl, alkoxycarbonyl, formyl, oxo, chloro, bromo, amine and nitro were tolerated in the aforesaid method. Excellent chemoselectivity was demonstrated through competition experiments.
Ghatak, Avishek,Khan, Sagar,Roy, Rimi,Bhar, Sanjay
supporting information
p. 7082 - 7088
(2015/02/02)

Betti base as an efficient ligand for copper-catalyzed ullmann coupling of phenol with aryl halides
GRAPHICAL ABSTRACT A simple, general, and highly efficient Betti base ligand has been developed for copper-catalyzed Ullmann coupling of phenol with aryl halides without the protection of an inert atmosphere. The reaction proceeds smoothly in the presence of K2CO3 as the base and dimethylsulfoxide as the solvent. The catalyst was reused several times with no evident loss of catalytic activity and is environmentally friendly.
Yang, Li,Yang, Qichao,Shi, Jianxin,Wang, Yufang,Zhang, Mingjie
supporting information
p. 2468 - 2477
(2014/08/05)

Graphene-supported Cu2O nanoparticles: An efficient heterogeneous catalyst for C-O cross-coupling of aryl iodides with phenols
Cu2O/graphene as a heterogeneous catalyst can effectively ignite and catalyze the Ullmann C-O cross-coupling of aryl iodides with phenols under mild conditions. The yield of diphenyl ether from the cross-coupling of phenol and iodobenzene can reach up to 96% at 150 °C in 3 h, and the turnover frequency can be as high as 1282 h-1. Meanwhile, the catalyst exhibits activity for varieties of C-O cross-coupling of aryl iodides, bromides and chlorides with phenol derivatives to form the corresponding aryl ethers. This journal is
Zhai, Zhaoyang,Guo, Xiaoning,Jiao, Zhifeng,Jin, Guoqiang,Guo, Xiang-Yun
p. 4196 - 4199
(2015/02/19)

Copper-mediated synthesis of mono- and dichlorinated diaryl ethers
An efficient synthesis of polychlorinated diphenyl ethers (PCDEs) using the Cu(OAc)2-catalyzed Chan-Lam coupling reaction is described. A library of all possible mono- and dichlorinated diphenyl ether congeners was prepared and characterized using MS, 1H, and 13C NMR spectroscopy, and Kovats retention indices. Our approach, using the optimized reaction conditions (i.e., reaction temperature, oxidizing atmosphere and base), significantly improves and simplifies the process compared to previously reported syntheses.
?ermák, Jan K.,Církva, Vladimír
supporting information
p. 4185 - 4188
(2014/07/22)

Iron(III)-mediated photocatalytic selective substitution of aryl bromine by chlorine with high chloride utilization efficiency
An iron(III)-mediated photocatalytic method for the conversion of aryl, heteroaryl and polycyclic aromatic bromides to the corresponding chlorides with high selectivity has been achieved successfully. The mild reaction conditions and high chloride utilization efficiency promise a bright future for chlorination reactions. The Royal Society of Chemistry 2014.
Wang, Ying,Li, Lina,Ji, Hongwei,Ma, Wanhong,Chen, Chuncheng,Zhao, Jincai
supporting information
p. 2344 - 2346
(2014/03/21)

Ligand free copper-catalyzed heterogeneous O-arylation reaction under green condition
A highly porous Zn-based iso-reticular metal-organic framework (IRMOF-3) has been selected for covalent modification. Pyridine-2-aldehyde has been used to decorate the free amine group of IRMOF-3 in the porous matrix. Schiff base moiety thus generated has been availed to anchor copper(II) ions to prepare the desired catalyst that catalyzes O-arylation reactions heterogeneously under mild reaction conditions. Porous catalyst demonstrates size selectivity in products when various substrates undergo O-arylation with α and β-naphthol.
Maity, Tanmoy,Saha, Debraj,Das, Soma,Bhunia, Susmita,Koner, Subratanath
p. 141 - 148
(2014/12/10)

Aminophenols as efficient ligand for copper-Catalyzed ullmann-Type synthesis of diaryl ethers
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Qian, Cunwei,Qin, Liang,Zong, Qianshou,Wu, Lin,Fang, Dong
supporting information
p. 3915 - 3918
(2014/01/17)

Palladium nanoparticles supported on silica diphenylphosphinite as efficient catalyst for C-O and C-S arylation of aryl halides
Silica diphenylphosphinite (SDPP) can be easily obtained through direct phosphorylation of silica gel. Further reaction of SDPP with Pd(II) produces nano Pd(0)/SDPP. This nano Pd(0) catalyst exhibits excellent reactivity for the C-O and C-S arylation of different aryl iodides, bromides and chloride with phenols and thiophenols. This heterogeneous catalyst shows excellent recyclability and can be easily recovered and reused for several runs. Copyright
Iranpoor, Nasser,Firouzabadi, Habib,Rostami, Abed
p. 501 - 506
(2013/09/23)

An in situ generated CuI/metformin complex as a novel and efficient catalyst for C-N and C-O cross-coupling reactions
An in situ generated complex of copper(I) and a biguanide, namely metformin, was found to be a highly efficient homogeneous catalyst in N/O-arylation reactions. The O-arylation of substituted phenols with various aryl iodides and bromides was also achieved using this copper catalyst to afford diaryl ethers in good to excellent yields in DMF. This heterogeneous copper catalyst also promotes the N-arylation of imidazole with a variety of aryl halides (Cl, Br, I) in acetonitrile.
Ghorbani-Vaghei, Ramin,Hemmati, Saba,Veisi, Hojat
p. 7095 - 7099
(2013/12/04)

First palladium-catalyzed denitrated coupling reaction of nitroarenes with phenols
The first palladium-catalyzed protocol for the denitrated coupling reaction of nitroarenes with phenols has been developed, achieving unsymmetrical diaryl ethers in moderate to excellent yields. The cyclopalladated ferrocenylimine (catalyst Ic) exhibited highly catalytic activity for this transformation with low catalyst loading (0.75 mol%) and short reaction time (2 h). The efficiency of this reaction was demonstrated by its compatibility with a range of groups. Moreover, the rigorous exclusion of air or moisture was not required in these transformations. Copyright
Wang, Hailei,Yu, Ajuan,Cao, Aijuan,Chang, Junbiao,Wu, Yangjie
p. 611 - 614
(2013/10/21)

Triphenyltin chloride as a new source of phenyl group for C-heteroatom and C-C bond formation
Ph3SnCl is introduced as a very suitable source of phenyl group for coupling with phenols, amines, and thiols in the presence of Cu(OAc)2 in Et3N at room temperature to give aryl ethers, amines, and arylthio ethers in high yields. In addition, the application of Ph3SnCl in the Stille coupling of aryl halides in the presence of Pd(0) catalyst in PEG 400 at 110C is discussed.
Iranpoor, Nasser,Firouzabadi, Habib,Elham, Etemadi Davan,Rostami, Abed,Nematollahi, Arash
p. 123 - 130
(2013/10/01)

Microwave-assisted synthesis of nonsymmetrical aryl ethers using nitro-arenes
An efficient, microwave-assisted ligand-free, catalyst-free synthetic method for nonsymmetrical diaryl ethers has been developed by using nitroarenes. A variety of phenols and nitroarenes was scanned by using this method to produce nonsymmetrical aryl ethers. The newly developed method is an ecofriendly and cost-effective approach to synthesize nonsymmetrical aryl ethers.
Sarkate, Aniket P.,Bahekar, Sushilkumar S.,Wadhai, Vijay M.,Ghandge, Ganesh N.,Wakte, Pravin S.,Shinde, Devanand B.
p. 1513 - 1516
(2013/08/23)