- Synthesis and characterization of nano-cellulose immobilized phenanthroline-copper (I) complex as a recyclable and efficient catalyst for preparation of diaryl ethers, N-aryl amides and N-aryl heterocycles
-
Functionalized nanocellulose was prepared and employed for immobilization of phenanthroline-copper(I) complex to afford cellulose nanofibril grafted heterogeneous copper catalyst [CNF-phen-Cu(I)]. This nanocatalyst was well characterized using FT-IR, NMR, XRD, CHNS, AAS, TGA, EDX and SEM. The activities of the synthesized catalyst were examined in the synthesis of diaryl ethers via C-O cross-coupling of phenols and aryl iodides, as well as, the preparation of N-aryl amides and N-aryl heterocycles through C-N cross-coupling of amides and N-H heterocycle compounds with aryl halides. In this trend, various substrates containing electron-donating and electron-withdrawing groups were exploited to evaluate the generality of this catalytic protocol. Accordingly, the catalyst demonstrated remarkable catalytic efficiency for both C-N and C-O cross-coupling reactions, thereby resulting in good to excellent yields of the desired products. Furthermore, the recoverability experiments of the catalyst showed that it can be readily retrieved by simple filtration and successfully reused several times with negligible loss of its catalytic activity.
- Aghili, Nora,Hosseinzadeh, Rahman,Mavvaji, Mohammad
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-
- Pd-Catalyzed Etherification of Nitroarenes
-
The Pd-catalyzed etherification of nitroarenes with arenols has been achieved using a new rationally designed ligand. Mechanistic insights were used to design the ligand so that both the oxidative addition and reductive elimination steps of a plausible catalytic cycle were facilitated. The catalytic system established here provides direct access to a range of unsymmetrical diaryl ethers from nitroarenes.
- Matsushita, Naoki,Kashihara, Myuto,Formica, Michele,Nakao, Yoshiaki
-
supporting information
p. 2209 - 2214
(2021/07/20)
-
- Aromatic ether compound or the sulfhydryl compound
-
[Problem] Aromatic ether compounds and aromatic sulfide compound of this new technology to[Solution] In general formula (1a), (1b), (1c) palladium or nickel compound or a phosphine compound represented by the compound comprising a transition metal compound in the presence of a transition metal catalyst, (A1) is represented by compounds having hydroxy carbon C a-OH or (A2) with a compound represented by the sulfhydryl carbon C a-SH, nitro group (- NO2 ) To react with an aromatic nitro compound (B), (A1) to the compound of the aromatic nitro compound (C1) or the reaction product of an aromatic ether compounds (B) hetero coupling (A2) of the compounds of the reaction product of an aromatic sulfide compound of an aromatic nitro compound (C2) generating (B) hetero coupling characterized by comprising the step of, aromatic ether compounds or aromatic sulfide compound. [Drawing] no
- -
-
Paragraph 0083-0084; 0109
(2021/11/19)
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- Oxalohydrazide Ligands for Copper-Catalyzed C?O Coupling Reactions with High Turnover Numbers
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Here, we report a class of ligands based on oxalohydrazide cores and N-amino pyrrole and N-amino indole units that generates long-lived copper catalysts for couplings that form the C?O bonds in biaryl ethers. These Cu-catalyzed coupling of phenols with aryl bromides occurred with turnovers up to 8000, a value which is nearly two orders of magnitude higher than those of prior couplings to form biaryl ethers and nearly an order of magnitude higher than those of any prior copper-catalyzed coupling of aryl bromides and chlorides. This ligand also led to copper systems that catalyze the coupling of aryl chlorides with phenols and the coupling of aryl bromides and iodides with primary benzylic and aliphatic alcohols. A wide variety of functional groups including nitriles, halides, ethers, ketones, amines, esters, amides, vinylarenes, alcohols and boronic acid esters were tolerated, and reactions occurred with aryl bromides in pharmaceutically related structures.
- Ray, Ritwika,Hartwig, John F.
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supporting information
p. 8203 - 8211
(2021/03/08)
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- Exhaustive Reduction of Esters Enabled by Nickel Catalysis
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We report a one-step procedure to directly reduce unactivated aryl esters into their corresponding tolyl derivatives. This is achieved by an organosilane-mediated ester hydrosilylation reaction and subsequent Ni/NHC-catalyzed hydrogenolysis. The resulting conditions provide a direct and efficient alternative to multi-step procedures for this transformation that often require the use of hazardous metal hydrides. Applications in the synthesis of -CD3-containing products, derivatization of bioactive molecules, and chemoselective reduction in the presence of other C-O bonds are demonstrated.
- Cook, Adam,Prakash, Sekar,Zheng, Yan-Long,Newman, Stephen G.
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supporting information
p. 8109 - 8115
(2020/05/20)
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- A novel magnetic polyacrylonotrile-based palladium Core?Shell complex: A highly efficientcatalyst for Synthesis of Diaryl ethers
-
The present article describes the synthesis of a new magnetic polyacrylonitrile-based Pd catalyst involving polyacrylonitrile modified via 2-aminopyridine as an efficient support to immobilize Pd nanoparticles. The simple reusability, easy separation and high stability of this Pd complex make it an excellent candidate to generate a C–O bond via Ph-X activation which is a really important subject in achieving biologically active compounds. It is worth to note access to good and high yields as well as broad substrate scope have resulted from superior reactivity of this catalyst complex. Furthermore, the structure of the magnetic polyacrylonitrile-based heterogeneous catalyst was characterized by fourier transmission infrared (FT-IR) spectroscopy, field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM), X-ray diffraction (XRD). Also, its thermal properties were studied by thermogravimetric analysis (TGA).
- Eslami, Mohammad,Jarahiyan, Atefeh,Moghaddam, Firouz Matloubi,Pourjavadi, Ali
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- 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
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p. 332 - 352
(2020/01/11)
-
- Preparation method of diaryl ether compound
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The invention relates to a preparation method of a diaryl ether compound. Particularly, under catalysis of chitosan supported cuprous oxide, an arylation reaction used for phenols is achieved, the corresponding diaryl ether compound is obtained, the technological condition is simple, the yield is good, operability is high, and wide functional group durability is achieved.
- -
-
Paragraph 0059; 0061; 0062; 0063
(2019/06/05)
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- Oxalic amide ligands, and uses thereof in copper-catalyzed coupling reaction of aryl halides
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The present invention provides oxalic amide ligands and uses thereof in copper-catalyzed coupling reaction of aryl halides. Specifically, the present invention provides a use of a compound represented by formula I, wherein definitions of each group are described in the specification. The compound represented by formula I can be used as a ligand in copper-catalyzed coupling reaction of aryl halides for the formation of C—N, C—O and C—S bonds.
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Page/Page column 98
(2020/01/09)
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- The First C?Cl Activation in Ullmann C?O Coupling by MOFs
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It was found that introduction of only 0.03 mol % Ag(I) into the framework of Cu3(BTC)2 ? xH2O in maghemite anchored CuBTC activated the inert CuBTC astonishingly to exhibit unexpected high catalytic activity for C?Cl activation in coupling of chloroarenes with phenols without the use of expensive ligands. This is the first application of mixed-metal MOFs in the C?X activation. Putting reusability and activity together, a TON over 15000 was obtained which is the highest TON compared with all its precedents even better than the results by Pd catalysts.
- Ramezani, Leila,Yahyazadeh, Asieh,Sheykhan, Mehdi
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p. 4636 - 4651
(2018/09/21)
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- Immobilized palladium nanoparticles on MNPs@A-N-AEB as an efficient catalyst for C-O bond formation in water as a green Solvent
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Palladium nanoparticles immobilized on the magnetic nanoparticles@2-amino-N-(2-aminoethyl) benzamide (MNPs@A-N-AEB.Pd0) have been presented as an efficient, and reusable magnetically heterogeneous catalyst for the C-O coupling reaction, namely Ullmann condensation reactions in an aqueous medium. This heterogeneous catalyst shows superior reactivity for the C-O arylation of different aryl halide (chloride, bromide, and iodide) with phenol derivatives to afford the desired products in good to excellent yields within short reaction time. Moreover, the catalyst can be easily recovered and reused for seven runs without loss of catalytic activity. The catalyst was characterized by several techniques, such as FT-IR, SEM, TEM, EDS, XRD, TGA and ICP-OES.
- Moghaddam, Firouz Matloubi,Eslami, Mohammad
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- N-Picolinamides as ligands in Ullman type C–O coupling reactions
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Copper-catalyzed modified Ullmann coupling reactions creating C–O bonds, including diaryl ethers or phenols, are vital to organic synthesis. Synthesized N-phenyl-2-pyridinecarboxamide and its derivatives were used as ligands in conjunction with catalytic copper sources in the formation of various diaryl ethers and phenols. Various aryl and heteroaryl halides with electron donating and withdrawing groups were reacted with various phenols under mild reaction conditions providing moderate to excellent yields.
- Damkaci, Fehmi,Sigindere, Cihad,Sobiech, Thomas,Vik, Erik,Malone, Joshua
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p. 3559 - 3564
(2017/10/05)
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- CATALYTIC SYSTEM FOR CROSS-COUPLING REACTIONS
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The present invention concerns a process for creating a Carbon-Carbon bond (C—C) or a Carbon-Heteroatom bond (C—HE) by reacting a compound carrying a leaving group with a nucleophilic compound carrying a carbon atom or a heteroatom (HE) that can substitute for the leaving group, creating a C—C or C—HE bond, wherein the reaction takes place in the presence of an effective quantity of a. a catalytic system comprising a ligand and at least a metal-based catalyst, such a metal catalyst being chosen among iron or copper compounds proviso that only a single metal is present.
- -
-
Paragraph 0303; 0304
(2016/06/06)
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- Copper and l-sodium ascorbate catalyzed hydroxylation and aryloxylation of aryl halides
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CuSO4·5H2O and NaAsc catalyzed hydroxylation and C-O/C-S cross-coupling reactions of aryl halides with phenols or 4-methylbenzenethiol were described. A wide range of substrates and test cases highlight the synthetic utility of the approach. A series of phenols, diaryl ethers, alkylaryl ethers, and diaryl thioethers were synthesized in high yield.
- Song, Guang-Lin,Zhang, Zhang,Da, Yu-Xia,Wang, Xi-Cun
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p. 8823 - 8829
(2015/10/20)
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- Maghemite-Copper Nanocomposites: Applications for Ligand-Free Cross-Coupling (C-O, C-S, and C-N) Reactions
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A magnetically retrievable, efficient, and benign maghemite-Cu nanocatalyst was synthesized from inexpensive precursors and applied for C-O, C-N, and C-S bond-formation reactions. The obtained maghemite-Cu nanocatalyst was characterized by various techniques such as XRD, X-ray photoelectron spectroscopy, field-emission gun SEM with energy-dispersive spectroscopy, atomic absorption spectroscopy, TEM, high-angle annular dark-field scanning transmission electron microscopy, FTIR spectroscopy, and M?ssbauer spectroscopy. Excellent catalytic activity, ease of recovery, and reusability without a significant loss of yield make the present protocol highly sustainable to deal with industrial and environmental concerns. Magnetic attraction: A magnetically retrievable, efficient, and benign maghemite-Cu nanocatalyst is synthesized from inexpensive precursors and applied for C-O, C-N, and C-S bond-formation reactions. Excellent catalytic activity, ease of recovery, and reusability without significant loss of yield make the present protocol highly sustainable to deal with industrial and environmental concerns.
- Sharma, Rakesh K.,Gaur, Rashmi,Yadav, Manavi,Rathi, Anuj K.,Pechousek, Jiri,Petr, Martin,Zboril, Radek,Gawande, Manoj B.
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p. 3495 - 3502
(2015/11/10)
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- A highly active and recyclable catalyst for the synthesis of indole and phenyl ether
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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
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p. 93463 - 93469
(2015/11/17)
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- Copper-catalyzed Ullmann-type synthesis of diaryl ethers assisted by salicylaldimine ligands
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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
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p. 337 - 340
(2014/02/14)
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- Ligand-free Ullmann-type C-heteroatom couplings under practical conditions
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A new practical ligand-free protocol for copper-catalyzed C-heteroatom cross-coupling reactions (Ullmann-type) is described. The use of dimethyl sulfoxide (DMSO) as the solvent overcomes the need to use organic auxiliary ligands; thus, DMSO is revealed as a nontoxic and superior solvent for Ullmann-type coupling reactions. This method allows the arylation of a wide range of amides, alcohols, and amines under practical conditions with bromobenzene and iodobenzene derivatives and will likely find direct application in current organic synthesis. The competitive reactivity among different functional groups is reported and rationalized, and the possibility to achieve selective arylation reactions is demonstrated. Copyright
- Gueell, Imma,Ribas, Xavi
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p. 3188 - 3195
(2014/06/09)
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- Synthesis of highly functionalized diaryl ethers by copper-mediated O-arylation of phenols using trivalent arylbismuth reagents
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Highly functionalized diaryl ethers were prepared by copper(II) acetate mediated O-arylation reaction of phenols using trivalent organobismuthanes. The reaction is performed under simple conditions and tolerates a wide diversity of functional groups on the phenol and on the organobismuth reagent. Substoichiometric amounts of catalyst can be used by performing the reaction under an oxygen atmosphere. The N-arylation of pyridones is also reported. Highly functionalized diaryl ethers were prepared by a copper(II) acetate mediated O-arylation reaction of phenols using trivalent organobismuthanes (see scheme). The reaction is performed under simple conditions and tolerates a wide diversity of functional groups on the phenol and on the organobismuth reagent. Substoichiometric amounts of catalyst can be used by performing the reaction under an oxygen atmosphere. The N-arylation of pyridones is also reported. FG=functional group.
- Crifar, Cynthia,Petiot, Pauline,Ahmad, Tabinda,Gagnon, Alexandre
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supporting information
p. 2755 - 2760
(2014/03/21)
-
- 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
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supporting information
p. 7082 - 7088
(2015/02/02)
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- KF/Clinoptilolite, an effective solid base in Ullmann ether synthesis catalyzed by CuO nanoparticles
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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
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- Palladium(II) thiosemicarbazone complex: Synthesis, structure and application to carbon-oxygen cross-coupling reaction
-
A simple route for the synthesis of square-planar palladium(II) 3-methyl-thiophene-2-aldehyde thiosemicarbazone complex is described. The composition of the complex has been established by elemental analysis and spectral methods. The molecular structure was confirmed by single crystal X-ray diffraction study. Further, the complex was used as a potential catalyst for the carbon-oxygen cross-coupling reaction of activating, non-activating and deactivating aryl iodides or aryl bromides with p-cresol.
- Suganthy, Pandimuni Kalpaga,Prabhu, Rupesh Narayana,Sridevi, Venugopal Shanmugham
-
-
- Carbon nanofiber supported copper nanoparticles catalyzed Ullmann-type coupling reactions under ligand-free conditions
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A carbon nanofiber supported copper nanoparticle (CuNP/CNF) catalyst was prepared and used for Ullmann-type couplings under ligand-free conditions. The catalyst exhibited high catalytic activity in C-O and C-N bond formation couplings. This journal is
- Li, Hongqiang,Li, Chunping,Bai, Jie,Zhang, Chenglin,Sun, Weiyan
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p. 48362 - 48367
(2014/12/10)
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- Facile preparation of unsymmetrical diaryl ethers from unsymmetrical diaryliodonium tosylates and phenols with high regioselectivity
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Unsymmetrical diaryl ethers were efficiently obtained in good yields by the reactions of aryl(4-methoxyphenyl)iodonium tosylates with phenols, and aryl(2,4-dimethoxyphenyl)iodonium tosylates with phenols, in the presence of potassium carbonate in acetonitrile, respectively. The latter iodonium tosylates provided the corresponding unsymmetrical diaryl ethers in good yields with high regioselectivities, together with the quantitative formation of 1-iodo-2,4-dimethoxybenzene. Georg Thieme Verlag Stuttgart New York.
- Kakinuma, Yohji,Moriyama, Katsuhiko,Togo, Hideo
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p. 183 - 188
(2013/02/23)
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- Methenamine as an efficient ligand for copper-catalyzed coupling of phenols with aryl halides
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Employing methenamine as a new supporting ligand, the copper-catalyzed coupling reactions of aryl bromides or aryl iodides with various phenols successfully proceeded in good yields under mild conditions. A series of diaryl ethers were obtained with excellent yields in the presence of K 3PO4 and copper(I) salt. Copyright
- Qian, Cunwei,Zong, Qianshou,Fang, Dong
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experimental part
p. 199 - 203
(2012/03/11)
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- Bis(μ-iodo)bis[(-)-sparteine]-dicopper: A versatile catalyst for direct O-Arylation and O-Alkylation of phenols and aliphatic alcohols with haloarenes
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The easy to prepare dimeric bis(μ-iodo)bis[(-)-sparteine]- dicopper ([CuI{(-)-spa}]2 complex) is shown to be versatile catalyst for O-arylation and O-alkylation with various aryl halides with phenols and aliphatic alcohols respectively, including less reactive aryl chlorides, such as chlorobenzene under mild conditions.
- Satyanarayana, Ponnam,Maheswaran, Hariharasarma,Kantam, Mannepalli Lakshmi,Bhargava, Suresh
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supporting information; experimental part
p. 788 - 790
(2011/08/22)
-
- New Catalytic System for Cross-Coupling Reactions
-
The present invention concerns a process for creating a Carbon-Carbon bond (C—C) or a Carbon-Heteroatom bond (C-HE) by reacting a compound carrying a leaving group with a nucleophilic compound carrying a carbon atom or a heteroatom (HE) that can substitute for the leaving group, creating a C—C or C-HE bond, wherein the reaction takes place in the presence of an effective quantity of a. a catalytic system comprising a ligand and at least a metal-based catalyst, such a metal catalyst being chosen among iron or copper compounds proviso that only a single metal is present.
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Page/Page column 13
(2012/01/03)
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- Rhodium(NHC)-catalyzed O -arylation of aryl bromides
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Chemical equations presented. The first example of the rhodium-catalyzed O-arylation of aryl bromides is reported. While the right combination of rhodium species and N-heterocyclic carbene (NHC) offered an effective catalytic system enabling the arylation to proceed, the choice of NHC was determined to be most important. The developed O-arylation protocol has a wide range of substrate scope, high functional group tolerance, and flexibility allowing a complementary route to either N- or O-arylation depending on the choice of NHC.
- Kim, Hyun Jin,Kim, Min,Chang, Sukbok
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supporting information; experimental part
p. 2368 - 2371
(2011/06/24)
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- Cross-coupling reactions of aryl halides with amines, phenols, and thiols catalyzed by an N,N′-dioxide-copper(I) catalytic system
-
The coupling reactions of various N, O, and S nucleophilic reagents with aryl halides have been successfully carried out under mild conditions by using a novel chiral N,N′-dioxide-copper(I) catalytic system as the catalyst. This versatile and efficient catalyst system has been demonstrated to facilitate the cross-coupling reactions of aryl halides with amines, phenols, and thiols to afford the corresponding desired products in good to excellent yields.
- Yang, Haitao,Xi, Chao,Miao, Zhiwei,Chen, Ruyu
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supporting information; experimental part
p. 3353 - 3360
(2011/08/03)
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- Potassium fluoride supported on natural nanoporous zeolite: A new solid base for the synthesis of diaryl ethers
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An efficient and inexpensive synthesis of diaryl ethers has been developed. The process involves the nucleophilic aromatic substitution of electron-deficient aryl halides and phenols and is mediated by potassium fluoride/Clinoptilolite (KF/CP) in dimethyl sulfoxide (DMSO). The approach affords good to excellent yields of the arylated products without the need for additional cation capture. The solid base is also efficient in the Ullmann ether synthesis. A new, inexpensive solid base for the synthesis of diaryl ethers has been developed. Clinoptilolite, a natural zeolite with a high tendency for cation capture, combined with potassium fluoride, provides an efficientsolid base for the deprotonation of phenols in nucleophilic reactions. The same solid base acts as a reliable base for the copper-catalyzed synthesis of diaryl ethers. Copyright
- Khalilzadeh, Mohammad A.,Hosseini, Abolfazl,Pilevar, Afsaneh
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experimental part
p. 1587 - 1592
(2011/04/22)
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- SUBSTITUTED IMIDAZOLONE DERIVATIVES, PREPARATIONS AND USES
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The present invention relates to polysubstituted imidazolone derivatives, to the pharmaceutical compositions comprising them and to the therapeutic uses thereof in the human and animal health fields. The present invention also relates to a process for preparing these derivatives.
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Page/Page column 55-56
(2010/02/16)
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- A recyclable heterogeneous copper(II) Schiff base catalyst for the O-arylation reaction of phenols with aryl halides
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Immobilisation of copper acetate onto a modified polystyrene provided a polymer-supported copper(II) Schiff base catalyst, which is effective in the O-arylation reaction of phenols with aryl halides to give diaryl ethers in high yields. This catalyst is air-stable and was recycled for five times with minimal loss of activity.
- Islam, Manirul,Mondal,Mondal,Roy,Mobarak,Hossain
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experimental part
p. 170 - 174
(2010/07/08)
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- Orthogonal Cu- and Pd-based catalyst systems for the O- and N-arylation of aminophenols
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O- or N-arylated aminophenol products constitute a common structural motif in various potentially useful therapeutic agents and/or drug candidates. We have developed a complementary set of Cu- and Pd-based catalyst systems for the selective O- and N-arylation of unprotected aminophenols using aryl halides. Selective O-arylation of 3- and 4-aminophenols is achieved with copper-catalyzed methods employing picolinic acid or CyDMEDA, trans-N,N′-dimethyl-1,2- cyclohexanediamine, respectively, as the ligand. The selective formation of N-arylated products of 3- and 4-aminophenols can be obtained with BrettPhos precatalyst, a biarylmonophosphine-based palladium catalyst. 2-Aminophenol can be selectively N-arylated with CuI, although no system for the selective O-arylation could be found. Coupling partners with diverse electronic properties and a variety of functional groups can be selectively transformed under these conditions.
- Maiti, Debabrata,Buchwald, Stephen L.
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supporting information; experimental part
p. 17423 - 17429
(2010/03/25)
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- General, mild, and intermolecular Ullmann-type synthesis of diaryl and alkyl aryl ethers catalyzed by diol-copper(I) complex
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(Chemical Equation Presented) A wide range of diaryl ethers and alkyl aryl ethers are synthesized through intermolecular C(aryl)-O bond formation from the corresponding aryl iodides/aryl bromides and phenols/alcohols through Ullmann-type coupling reaction in the presence of a catalytic amount of easily available (±)-diol L3-CuI complex under very mild reaction conditions. Less reactive aryl bromides can also be used for O-arylation of phenols under the same reaction conditions without increasing the reaction temperature, catalyst loading, and time. The catalytic system not only is capable of coupling hindered substrate but also tolerates a broad range of a series of functional groups.
- Naidu, Ajay B.,Jaseer,Sekar, Govindasamy
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supporting information; experimental part
p. 3675 - 3679
(2009/09/26)
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- Trinuclear copper(I) complexes with triscarbene ligands: Catalysis of C-N and C-C coupling reactions
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Novel synthetic routes for the preparation of trinuclear copper(I) complexes with triscarbene ligands are presented, which yield higher purity products than the one previously described. The first crystal structure of one of these complexes is reported an
- Biffis, Andrea,Tubaro, Cristina,Scattolin, Elena,Basato, Marino,Papini, Grazia,Santini, Carlo,Alvarez, Eleuterio,Conejero, Salvador
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experimental part
p. 7223 - 7229
(2010/02/15)
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- Copper(I)-catalyzed C-C and C-O coupling reactions using hydrazone ligands
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Copper-catalyzed C-C coupling reaction of aryl iodides with diethylmalonate in toluene at 90C gave arylated malonates using 5 mol% of CuI with hydrazone 1a as a ligand in good yields under an aerobic atmosphere. We also found CuI/hydrazone 1b in toluene to be an efficient catalytic system for C-O coupling reactions of aryl bromides with phenols to give aryl ethers in good yields at 110C under an aerobic atmosphere.
- Mino, Takashi,Yagishita, Fumitoshi,Shibuya, Masanori,Kajiwara, Kenji,Shindo, Hiroaki,Sakamoto, Masami,Fujita, Tsutomu
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experimental part
p. 2457 - 2460
(2010/01/07)
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- Glyoxal bis(phenylhydrazone) as promoter for CuI-catalyzed O-arylation of phenols with bromoarenes
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A very simple bishydrazone-type ligand, glyoxal bis(phenylhydrazone) (L1), was found to effectively promote the CuI-catalyzed O-arylation of phenols with aryl bromides. This cross-coupling reaction proceeded in acetonitrile at 60-80 °C in the presence of K3PO4 as base. A diverse array of phenols and bromoarenes was employed as substrates to afford diaryl ethers in good to excellent yields, and some base-sensitive groups, such as ester, aldehyde, and ketone groups, can survive under the mild reaction conditions.
- Liu, Yu-Hua,Li, Gang,Yang, Lian-Ming
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experimental part
p. 343 - 346
(2009/04/19)
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- Copper- or iron-catalyzed arylation of phenols from respectively aryl chlorides and aryl iodides
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The utility of diketone-1 was checked, which was first introduced for bimetallic Fe-Cu catalysts, in copper-catalyzed arylation of phenols from aryl chlorides. A systematic study was first undertaken by choosing 3,5-dimethylphenol as a model substrate. The first blank test was undertaken with PhCl and the dieketone-1/[Cu(acac)2] system. The second blank test was performed without copper and showed as expected that the arylation from PhCl did not proceed at all with a catalytic system only based on iron. A protocol permitting the arylation of 3,5-dimethylphenol with chlorobenzene in excellent yield. The system diketone-1//[Cu(acac)2] efficiently promotes cross-coupling reactions between phenols and chlorobenzene or aryl chlorides, which are deactivated by electron-donating substituents. The results indicate that an efficient global method for arylation of phenols from aromatic chlorides can be discovered.
- Xia, Ning,Taillefer, Marc
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supporting information; scheme or table
p. 6037 - 6039
(2009/05/27)
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- Palladium N-heterocyclic carbene catalysts for synthesis of diaryl ethers
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Novel functionalized 1,3-dialkylimidazolinium (LH) salts as precursors for N-heterocyclic carbenes (NHCs) have been prepared and successfully applied in the palladium-catalyzed synthesis of diaryl ethers and arylation of benzaldehydes. An efficient cataly
- Akko?, Mitat,Gürbüz, Nevin,?etinkaya, Engin,?zdemir, Ismail
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experimental part
p. 1781 - 1784
(2009/04/11)
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- Method for Producing Aryl Amines, Aryl Ethers and Aryl Thioethers
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The invention relates to a method for producing aryl or heteroaryl amines, ethers or thioethers (III) by cross-coupling primary or secondary amities, alcohols or thioalcohols with substituted aryl or heteroaryl compounds (I) in the presence of a Br?nsted
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Page/Page column 8
(2009/01/20)
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- Synthesis of diaryl ethers through the copper-catalyzed arylation of phenols with aryl iodides using KF/Al2O3
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An efficient synthesis of diaryl ethers by the copper-catalyzed arylation of phenols with a variety of aryl iodide susing KF/Al2O3 as a suitable base and CuI and 1,3 diphenyl-1,3 propandione as the catalyst is described. Copyright Taylor & Francis Group, LLC.
- Hosseinzadeh, Rahman,Tajbakhsh, Mahmood,Mohadjerani, Maryam,Rezaei, Parizad,Alikarami, Mohammad
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p. 3023 - 3031
(2008/12/23)
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- An efficient BINAM-copper(II) catalyzed Ullmann-type synthesis of diaryl ethers
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A wide range of diaryl ethers are synthesized from the corresponding aryl iodides and phenols through Ullmann type coupling reactions in the presence of a catalytic amount of easily available BINAM-Cu(OTf)2 complex under mild reaction conditions. Less reactive aryl bromides have also been shown to react with phenols under identical reaction conditions to give good yields of the diaryl ethers without increasing the reaction temperature and time.
- Naidu, Ajay B.,Raghunath,Prasad,Sekar
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p. 1057 - 1061
(2008/09/18)
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- Copper-catalyzed Ullmann coupling under ligand- and additive- free conditions. Part 1: O-Arylation of phenols with aryl halides
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O-Arylation of a wide variety of substituted phenols and aliphatic alcohols with aryl halides catalyzed by copper iodide under mild ligand and additive free conditions (nBu4NBr, DMF, K3PO4, reflux, 22 h) is accomplished in good to excellent product yields (up to 95%).
- Chang, Joyce Wei Wei,Chee, Sheena,Mak, Shiya,Buranaprasertsuk, Pongchart,Chavasiri, Warinthorn,Chan, Philip Wai Hong
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p. 2018 - 2022
(2008/09/19)
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- Efficient catalysis of Ullmann-type arylation reactions by a novel trinuclear copper(I) complex with a chelating tricarbene ligand
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A novel trinuclear copper(I) complex with a chelating tricarbene ligand is shown to be an efficient catalyst for the arylation of different classes of compounds containing N-H or O-H functions. Different kinds of azole rings (pyrazole, imidazole, 1,2,4-triazole) can be arylated with comparable efficiencies at relatively mild temperatures (100 °C). The catalyst activates aryl iodides, bromides and even chlorides for the reaction. An unusually strong influence of the nature of the aryl substituent on the reaction yield is observed. The synthetic protocol can be extended to other substrate classes, such as phenols and amides, although the catalytic efficiency with amides is significantly reduced.
- Tubaro, Cristina,Biffis, Andrea,Scattolin, Elena,Basato, Marino
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p. 4187 - 4195
(2008/09/20)
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- An efficient Ullmann-type C-O bond formation catalyzed by an air-stable copper(I)-bipyridyl complex
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(Chemical Equation Presented) An efficient O-arylation of phenols and aliphatic alcohols with aryl halides was developed that uses an air-stable copper(I) complex as the catalyst. This arylation reaction can be performed in good yield in the absence of Cs2CO3. A variety of functional groups are compatible with these reaction conditions with low catalyst loading levels.
- Niu, Jiajia,Zhou, Hua,Li, Zhigang,Xu, Jingwei,Hu, Shaojing
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p. 7814 - 7817
(2008/12/22)
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- Facile synthesis of 9-azajulolidine and its application to post-Ullmann reactions
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This Letter describes the efficient synthesis of 9-azajulolidine from readily available reagents and its utilization as an effective electron-rich ligand for post-Ullmann-type reactions, that is, for C(aryl)-heteroatom (N, O, S) bond formation reactions, with dramatically enhanced reaction rates.
- Wong, Ken-Tsung,Ku, Sung-Yu,Yen, Feng-Wen
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p. 5051 - 5054
(2008/02/12)
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- BIARYL SUBSTITUTED HETEROCYCLE INHIBITORS OF LTA4H FOR TREATING INFLAMMATION
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The present invention relates to a chemical genus of biaryl substituted heterocycle inhibitors of LTA4H (leukotriene A4 hydrolase) useful for the treatment and prevention and prophylaxis of inflammatory diseases and disorders. The compounds have general formula Ψ: An example is
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Page/Page column 25; 34
(2008/06/13)
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- A general and efficient protocol for the synthesis of biaryl ethers from aryl silyl ethers using Cs2CO3
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A general and efficient one-step procedure has been developed for the synthesis of biaryl ethers via direct coupling of electron-deficient arylhalides or aryl triflates to aryl t-butyldimethylsilyl (TBS) ethers using Cs 2CO3. The protocol was also applied to electron-rich arylhalides by addition of a catalytic amount of copper(I) iodide. The reaction is rapid and provides good to excellent yields.
- Cui, Sun-Liang,Jiang, Zhi-Yong,Wang, Yan-Guang
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p. 1829 - 1831
(2007/10/03)
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- Air stable, sterically hindered ferrocenyl dialkylphosphines for palladium-catalyzed C-C, C-N, and C-O bond-forming cross-couplings
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Pentaphenylferrocenyl di-tert-butylphosphine has been prepared in high yield from a two-step synthetic procedure, and the scope of various cross-coupling processes catalyzed by complexes bearing this ligand has been investigated. This ligand creates a remarkably general palladium catalyst for aryl halide amination and for Suzuki coupling. Turnovers of roughly 1000 were observed for aminations with unactivated aryl bromides or chlorides. In addition, complexes of this ligand catalyzed the formation of selected aryl ethers under mild conditions. The reactions encompassed electron-rich and electron-poor aryl bromides and chlorides. In the presence of catalysts containing this ligand, these aryl halides coupled with acyclic or cyclic secondary alkyl- and arylamines, with primary alkyl- and arylamines, and with aryl- and primary alkylboronic acids. These last couplings provide the first general procedure for reaction of terminal alkylboronic acids with aryl halides without toxic or expensive bases. The ligand not only generates highly active palladium catalysts, but it is air stable in solution and in the solid state. Palladium(0) complexes of this ligand are also air stable as a solid and react only slowly with oxygen in solution.
- Kataoka, Noriyasu,Shelby, Quinetta,Stambuli, James P.,Hartwig, John F.
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p. 5553 - 5566
(2007/10/03)
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