- Enhanced catalytic properties of copper in O- and N-arylation and vinylation reactions, using phosphorus dendrimers as ligands
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Imino pyridine-capped phosphorus dendrimers were found to strongly enhance the catalytic activity of copper in arylations and vinylations of O- and N-nucleophiles. These reactions could indeed be performed under very mild conditions, often the mildest to
- Ouali, Armelle,Laurent, Regis,Caminade, Anne-Marie,Majoral, Jean-Pierre,Taillefer, Marc
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Read Online
- Effect of water in fabricating copper nanoparticles onto reduced graphene oxide nanosheets: Application in catalytic ullmann-coupling reactions
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Copper nanoparticles fabricated onto reduced graphene oxide (Cu NPs/rGO) were successfully synthesized via a one-pot dimethylformamide (DMF) reduction approach with an addition of nominal water. This small amount of water can significantly decrease the de
- Kondo, Ryota,Leeladee, Pannee,Nagata, Tatsuki,Obora, Yasushi,Suktanarak, Pattira,Suzuki, Takeyuki,Tanaka, Tatsuya,Tuntulani, Thawatchai
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Read Online
- Ligand- and Counterion-Assisted Phenol O-Arylation with TMP-Iodonium(III) Acetates
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High reactivity of trimethoxyphenyl (TMP)-iodonium(III) acetate for phenol O-arylation was achieved. It was first determined that the TMP ligand and acetate anion cooperatively enhance the electrophilic reactivity toward phenol oxygen atoms. The proposed method provides access to various diaryl ethers in significantly higher yields than the previously reported techniques. Various functional groups, including aliphatic alcohol, boronic ester, and sterically hindered groups, were tolerated during O-arylation, verifying the applicability of this ligand- and counterion-assisted strategy.
- Kikushima, Kotaro,Miyamoto, Naoki,Watanabe, Kazuma,Koseki, Daichi,Kita, Yasuyuki,Dohi, Toshifumi
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p. 1924 - 1928
(2022/03/27)
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- Solvent-free palladium-catalyzed C–O cross-coupling of aryl bromides with phenols
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A new solvent-free procedure for C–O cross-coupling between phenols and aryl bromides comprising of Pd2(dba)3/ButBrettPhos catalytic system is efficient for substrates bearing donor or acceptor, as well as bulky substituents.
- Asachenko, Andrey F.,Bogachev, Vasilii N.,Cherkashchenko, Ilia R.,Lavrov, Konstantin V.,Minaeva, Lidiya I.,Nechaev, Mikhail S.,Rzhevskiy, Sergey A.,Sterligov, Grigorii K.,Topchiy, Maxim A.
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p. 409 - 411
(2021/06/07)
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- Ligand compound for copper catalyzed aryl halide coupling reaction, catalytic system and coupling reaction
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The invention provides a ligand compound capable of being used for copper catalyzed aryl halide coupling reaction, the ligand compound is a three-class compound containing a 2-(substituted or non-substituted) aminopyridine nitrogen-oxygen group, and the invention also provides a catalytic system for the aryl halide coupling reaction. Thecatalytic system comprises a copper catalyst, a compound containing a 2-(substituted or non-substituted) aminopyridine nitrogen-oxygen group adopted as a ligand, alkali and a solvent, and meanwhile, the invention also provides a system for the aryl halide coupling reaction adopting the catalyst system. The compound containing the 2-(substituted or non-substituted) aminopyridine nitrogen oxygen group can be used as the ligand for the copper catalyzed aryl chloride coupling reaction, and the ligand is stable under a strong alkaline condition and can well maintain catalytic activity when being used for the copper-catalyzed aryl chloride coupling reaction. In addition, the copper catalyst adopting the compound as the ligand can particularly effectively promote coupling of copper catalyzed aryl chloride and various nucleophilic reagents which are difficult to generate under conventional conditions, C-N, C-O and C-S bonds are generated, and numerous useful small molecule compounds are synthesized. Therefore, the aryl halide coupling reaction has a very good large-scale application prospect by adopting the copper catalysis system of the ligand.
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Paragraph 0134-0139
(2021/05/29)
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- Fabrication of Metal Nanoparticle Composites by Slow Chemical Reduction of Metal-Organic Frameworks
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Constructing metal nanoparticle (MNP) composites from metal-organic framework (MOF) precursors has attracted extensive attention as the MOF precursors provide an excellent porous matrix for the generation of MNP composites, which enables the direct fabric
- Fu, Yu,Zhai, Xu,Wang, Sha,Shao, Lei,Bai, Xiao-Jue,Su, Ze-Shun,Liu, Yun-Ling,Zhang, Li-Ying,Chen, Jun-Yi
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p. 16447 - 16454
(2021/11/04)
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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
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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)
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- Design of BNPs-TAPC Palladium Complex as a Reusable Heterogeneous Nanocatalyst for the O-Arylation of Phenols and N-Arylation of Amines
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The thermally stable new heterogenous nanocatalyst BNPs@SiO2(CH2)3-TAPC-O-CH2CH2NH2-Pd(0) was synthesized, characterized and successfully applied in carbon-heteroatom (C–O and C–N) coupling reactions of aryl halides with phenols and amines. The formation of resultant nanocatalyst was approved by FT-IR, XRD, TGA, XPS and EDX techniques. The morphology of BNPs@SiO2(CH2)3-TAPC-O-CH2CH2NH2-Pd(0) was characterized using scanning and transmission electron microscopes. The leaching of palladium from the surface of the catalyst was studid by ICP-OES technique. Noteworthy, the highly active BNPs@SiO2(CH2)3-TAPC-O-CH2CH2NH2-Pd(0) can be easily recycled and reused for six times with negligible loss in its activity. Some remarkable advantages of this method are the shorter reaction times, milder conditions, no needs for an inert atmosphere, high yields and easy separation. Graphical Abstract: [Figure not available: see fulltext.].
- Bahrami, Kiumars,Khodamorady, Minoo
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p. 688 - 698
(2019/01/04)
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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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- Copper(I)-USY as a Ligand-Free and Recyclable Catalyst for Ullmann-Type O-, N-, S-, and C-Arylation Reactions: Scope and Application to Total Synthesis
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The copper(I)-doped zeolite CuI-USY proved to be a versatile, efficient, and recyclable catalyst for various Ullmann-type coupling reactions. Easy to prepare and cheap, this catalytic material enables the arylation and heteroarylation of diverse O-, N-, S-, and C-nucleophiles under ligand-free conditions while exhibiting large functional group compatibility. The facility of this catalyst to promote C-O bond formation was further demonstrated with the total synthesis of 3-methylobovatol, a naturally occurring diaryl ether of biological relevance. From a mechanistic viewpoint, two competitive pathways depending on the nature of the nucleophile and consistent with the obtained results have been proposed.
- Garnier, Tony,Danel, Mathieu,Magné, Valentin,Pujol, Anthony,Bénéteau, Valérie,Pale, Patrick,Chassaing, Stefan
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p. 6408 - 6422
(2018/05/31)
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- 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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supporting information
p. 3559 - 3564
(2017/10/05)
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- Ullmann reaction through ecocatalysis: Insights from bioresource and synthetic potential
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We report the elaboration of novel bio-sourced ecocatalysts for the Ullmann coupling reaction. Ecocatalysis is based on the recycling of metals issued from phytoremediation or rehabilitation, and an innovative chemical valorization of the subsequent biomass in the field of catalysis. Here, we describe efficient copper accumulation by plants via phytoextraction and rhizofiltration. These phytotechnologies were revisited to demonstrate a novel potential of these natural resources for green chemistry. Taking advantage of the remarkable ability of the selected plants to accumulate Cu(ii) species into their roots or leaves, the latter can be directly used for the preparation of ecocatalysts, called Eco-Cu. The formed Eco-Cu catalysts are thoroughly characterized via ICP-MS, IR studies of pyridine sorption/desorption, TEM, XRD, SM and model reactions, in order to elucidate the chemical composition and catalytic activity of these new materials. Significant differences of properties and activities were observed between Eco-Cu and conventional Cu catalysts. Eco-Cu are highly active catalysts in Ullmann coupling reactions with lower Cu quantities compared to known copper catalysts.
- Clavé, Guillaume,Garel, Claire,Poullain, Cyril,Renard, Brice-Lo?c,Olszewski, Tomasz K.,Lange, Bastien,Shutcha, Mylor,Faucon, Michel-Pierre,Grison, Claude
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p. 59550 - 59564
(2016/07/06)
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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.
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Paragraph 0305; 0306
(2016/06/06)
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- Green alternative solvents for the copper-catalysed arylation of phenols and amides
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Investigation of the use of green organic solvents for the Cu-catalysed arylation of phenols and amides is reported. Alkyl acetates proved to be efficient solvents in the catalytic processes, and therefore excellent alternatives to the typical non-green solvents used for Cu-catalysed arylation reactions. Solvents such as isosorbide dimethyl ether (DMI) and diethyl carbonate also appear to be viable possibilities for the arylation of phenols. Finally, a novel copper catalysed acyl transfer process is reported.
- Sambiagio, Carlo,Munday, Rachel H.,John Blacker,Marsden, Stephen P.,McGowan, Patrick C.
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p. 70025 - 70032
(2016/08/06)
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- Orthogonal Discrimination among Functional Groups in Ullmann-Type C-O and C-N Couplings
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The copper-catalyzed arylation of nucleophiles has been established as an efficient methodology for the formation of C-C and C-heteroatom bonds. Considering the advances during the last two decades, the ligand choice plays a key role in such transformations and can strongly influence the catalytic efficiency. The applicability of these Ullmann-type coupling reactions regarding the orthogonal selectivity of different functional groups constitutes a challenging subject for current synthetic strategies. Herein, we report a useful toolkit of Cu-based catalysts for the chemoselective arylation of a wide-range of nucleophiles in competitive reactions using aryl iodides and bromides. We show in this work that the arylation of all kinds of amides can be orthogonal to that of amines (aliphatic or aromatic) and phenol derivatives. This high chemoselectivity can be governed by the use of different ligands, yielding the desired coupling products under mild conditions. The selectivity trends are maintained for electronically biased iodobenzene and bromobenzene electrophiles. Radical clock experiments discard the occurrence of radical-based mechanisms.
- Rovira, Mireia,Soler, Marta,Güell, Imma,Wang, Ming-Zheng,Gómez, Laura,Ribas, Xavi
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supporting information
p. 7315 - 7325
(2016/09/09)
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- CuI-USY as a Ligand-Free and Recyclable Catalytic System for the Ullmann-Type Diaryl Ether Synthesis
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The catalytic potential of copper(I)-exchanged zeolites was evaluated in the Ullmann-type synthesis of diaryl ethers. Among four investigated zeolites (i.e., USY, MOR, β, and ZSM5), CuI-USY was the best catalyst and proved efficient under ligand-free conditions in toluene at 120 °C. CuI-USY was also easy to recover and was recyclable up to five times without significant loss of activity.
- Magné, Valentin,Garnier, Tony,Danel, Mathieu,Pale, Patrick,Chassaing, Stefan
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supporting information
p. 4494 - 4497
(2015/09/28)
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- USE OF COMPOSITIONS OBTAINED BY CALCINING PARTICULAR METAL-ACCUMULATING PLANTS FOR IMPLEMENTING CATALYTICAL REACTIONS
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The use of metal-accumulating plants for implementing chemical reactions especially catalytical reactions.
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Paragraph 0868; 0870
(2016/01/25)
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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)
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- Microwave-assisted synthesis of nonsymmetrical aryl ethers using nitro-arenes
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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.
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p. 1513 - 1516
(2013/08/23)
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- Preparation of carbon nanotube-supported α-Fe2O 3@CuO nanocomposite: A highly efficient and magnetically separable catalyst in cross-coupling of aryl halides with phenols
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Herein, we introduce the first magnetic CuO nanoparticles based on carbon nanotubes as a highly intriguing magnetic catalyst in Ullmann-type coupling of aryl halides with phenols. Two facile procedures were used for the preparation of this magnetically separable catalytic system. Having been treated with FeSO4 and then H2O2, nanotubes accommodated the resulting iron hydroxides on the walls. The resulting nanocomposite was then exposed to argon atmosphere at 450°C giving rise to a carbon nanotube-supported α-Fe2O3 compound. Ultimately, copper acetate was hydrolysed in the presence of CNT supported α-Fe 2O3 at 100°C and our novel catalyst was gained. Some spectroscopic and microscopic techniques such as Infrared spectroscopy (IR), X-ray diffraction spectroscopy (XRD), Vibrational sample magnetometry (VSM), Brunauer-Emmett-Teller (BET), Barrett-Joyner-Halenda (BJH), Inductively coupled plasma (ICP), Scanning electron microscopy (SEM) and Transmission electron microscopy (TEM) corroborated the structure of the catalyst. The catalyst synthesized showed good activity in C-O cross coupling reactions affording the highest rate of completion. Magnetic feature of the catalyst helped facile separation of it from the reaction medium. The catalyst could also be reused up to six times without any loss of its activity.
- Saberi, Dariush,Sheykhan, Mehdi,Niknam, Khodabakhsh,Heydari, Akbar
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p. 2025 - 2031
(2013/07/26)
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- Synthesis of dendritic β-diketones and their application in copper-catalyzed diaryl ether formation
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Phosphorus-based dendrimers decorated with β-diketones were prepared and fully characterized. These macromolecules, which are the first examples of multivalent dendrimeric β-diketones, were tested as ligands for copper in O-arylations of 3,5-dimethylpheno
- Keller, Michel,Ianchuk, Mykhailo,Ladeira, Sonia,Taillefer, Marc,Caminade, Anne-Marie,Majoral, Jean-Pierre,Ouali, Armelle
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supporting information; experimental part
p. 1056 - 1062
(2012/04/10)
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- Surfactant-free single-nano-sized colloidal Cu nanoparticles for use as an active catalyst in Ullmann-coupling reaction
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Surfactant-free, single-nano-sized copper nanoparticles (Cu NPs) (size: about 2 nm) were prepared by the DMF reduction method. The Cu NPs showed high catalytic activity (with a turnover number (TON) of up to 2.2 × 10 4) in Ullmann-type cross-coupling of aryl halides with phenols under ligand-free conditions. The Royal Society of Chemistry 2012.
- Isomura, Yuto,Narushima, Takashi,Kawasaki, Hideya,Yonezawa, Tetsu,Obora, Yasushi
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supporting information; experimental part
p. 3784 - 3786
(2012/06/16)
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- Highly efficient copper catalytic system for the O-arylation of phenol with iodoarene
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An efficient Cu-catalyzed O-arylation was carried out by involving phenols with iodoarenes to afford various substituted diarylether derivatives with tiny loading of Cu2O and 1H-imidazole-4-carboxylic acid as catalytic system under mild conditions, which provided good to excellent yields with good tolerance of functional groups.
- Cheng, An-Yi,Hsieh, Jen-Chieh
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supporting information; experimental part
p. 71 - 75
(2012/01/31)
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- Efficient iron/copper-cocatalyzed o-arylation of phenols with bromoarenes
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Low catalytic amount CuI and Fe(acac)3 were found to effectively promote the C-O cross-coupling reaction in the presence of K2CO 3 as the base. A serious of diaryl ethers with different substitutents can be synthesized in good to excellent yields. This efficient and economic method is attractive for applications on an industrial scale. Georg Thieme Verlag Stuttgart New York.
- Liu, Xiaoyan,Zhang, Songlin
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supporting information; experimental part
p. 268 - 272
(2011/03/20)
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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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- New 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.
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(2012/01/03)
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- Recyclable heterogeneous copper oxide on alumina catalyzed coupling of phenols and alcohols with aryl halides under ligand-free conditions
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An efficient alumina-supported CuO-catalyzed O-arylation of phenols and aliphatic alcohols with various aryl as well as heteroaryl halides under ligand-free conditions are reported. This protocol provides a variety of diaryl ether and bis-diaryl ether motifs by reacting different aryl/aliphatic halides with differently substituted phenols and saturated alcohols in the presence of a catalytic amount of CuO on alumina and KOH as a base at moderate temperature under nitrogen atmosphere. The described methodology is simple, straightforward and efficient to afford the cross-coupled products in high yields under ligand-free conditions. The explored catalyst is inexpensive, air-stable and recyclable up to three cycles.
- Swapna, Kokkirala,Murthy, Sabbavarapu Narayana,Jyothi, Mocharla Tarani,Nageswar, Yadavalli Venkata Durga
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supporting information; experimental part
p. 5978 - 5988
(2011/10/05)
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- Aminoarenethiolato-copper(I) as (pre-)catalyst for the synthesis of diaryl ethers from aryl bromides and sequential C-O/C-S and C-N/C-S cross coupling reactions
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A small library of 2-aminoarenethiolato-copper(I) (CuSAr) complexes was tested as (pre-)catalysts in the arylation reaction of phenols with aryl bromides. These copper(I) (pre-)catalysts are thermally stable, soluble in common organic solvents, and allow reactions of 6 h at 160 °C with low catalyst loadings of 2.5 mol %. Among the (pre-)catalysts screened, 2-[(dimethylamino)methyl]benzenethiolato-copper(I) (1c) led to the best results and provided good to excellent yields of various substituted diaryl ethers. Mechanistic studies showed that at early stages of the C-O coupling reaction the CuSAr complex is converted into CuBr(PhSAr) via selective coupling of the monoanionic arenethiolato ligand with phenyl bromide with formation of CuBr. In addition, the first results are shown involving a multi-component reaction (MCR) protocol for the in situ synthesis of propargylamines and their subsequent conversion involving a C-O cross coupling reaction. Furthermore, two examples of sequential C-O/C-S and C-N/C-S cross coupling reactions have been carried out on the same dihalo-pyridine substrate in a one-pot process with the same (CuSAr) (pre-)catalyst (overall yields 40-80%).
- Sperotto, Elena,Van Klink, Gerard P.M.,De Vries, Johannes G.,Van Koten, Gerard
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experimental part
p. 9009 - 9020
(2011/01/04)
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- METHOD FOR THE PREPARATION OF PHOSPHINE BUTADIENE LIGANDS, COMPLEXES THEREOF WITH COPPER AND USE THEREOF IN CATALYSIS
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The present invention relates to a method for preparing phosphine butadiene-type ligands, and their use, particularly as catalytic metal ligands used in the reactions leading to the formation of carbon-carbon and carbon-heteroatom bonds.
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Page/Page column 19; 20
(2010/06/11)
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- Sol-gel immobilized and reusable copper-catalyst for arylation of phenols from aryl bromides
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A simple β-diamide ligand was immobilized by the sol-gel process on hybrid silica for Cu-mediated O-arylation reactions. Combined with 5% of CuI, the latter can easily be recovered and reused to generate diarylethers under smooth conditions from cheap aryl bromides in an eco-friendly solvent (MIBK). Besides, negligible metal leaching occurred after reaction in solution from the supported catalyst.
- Benyahya, Sofia,Monnier, Florian,Wong Chi Man, Michel,Bied, Catherine,Ouazzani, Fouad,Taillefer, Marc
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supporting information; experimental part
p. 1121 - 1123
(2010/05/02)
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- Copper-catalyzed arylation of nucleophiles by using butadienylphosphines as ligands: Mechanistic insight
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(Figure Presented) Worth diene for: The butadienylphosphine L (see scheme), obtained on a large scale from a new synthetic method, is an efficient ligand in Ullmann-type copper-catalyzed arylation reactions. The use of this phosphorus ligand made it possible to follow the reaction by 31P NMR spectroscopy and thus to propose a mechanism for the Ullmann reaction.
- Kaddouri, Hamid,Vicente, Virginie,Ouali, Armelle,Ouazzani, Fouad,Taillefer, Marc
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supporting information; experimental part
p. 333 - 336
(2009/04/14)
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- Method for forming a carbon-carbon or carbon-heteroatom bond
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The invention relates to a method for forming a carbon-carbon or carbon-heteroatom bond by reacting an unsaturated compound carrying a leaving group and a nucleophilic compound, in the absence of a ligand. The aim of the invention is especially to form carbon-nitrogen bonds according to a method for the arylation of nitrogenated organic derivatives. According to the inventive method, a carbon-carbon or carbon-heteroatom bond is formed by reacting an unsaturated compound carrying a leaving group with a nucleophilic compound donating a carbon atom or a heteroatom (HE) that can substitute the leaving group, thus forming a C—C or C—HE bond, in the presence of a copper-based catalyst and a base. Said metal is characterised in that the reaction takes place in the absence of a ligand and in a nitrile-type solvent.
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Page/Page column 13
(2009/10/01)
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- (2-Pyridyl)acetone-promoted Cu-catalyzed O-arylation of phenols with aryl iodides, bromides, and chlorides
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(Chemical Equation Presented) Employing (2-pyridyl)acetone as a new supporting ligand, the copper-catalyzed coupling reactions of aryl chlorides, aryl bromides, and aryl iodides with various phenols successfully proceeded in good yields under mild conditions. This reaction displays great functional groups compatibility and excellent reactive selectivity.
- Zhang, Qi,Wang, Deping,Wang, Xianyang,Ding, Ke
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supporting information; experimental part
p. 7187 - 7190
(2009/12/09)
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- IRON-COPPER CO-CATALYZED PROCESS FOR CARBON-CARBON OR CARBON-HETEROATOM BONDING
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The present invention relates to 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 catalytic system comprising iron and copper.
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Page/Page column 52
(2008/06/13)
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- Efficient and versatile sol-gel immobilized copper catalyst for ullmann arylation of phenols
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A new hybrid silica with urea-based bipyridyl bridging units has been synthesized by a solgel process. The copper-complexed hybrid silica is an efficient heterogeneous catalyst for the Ullmann coupling of aryl halides with phenols. It is easily withdrawn and recovered from the reaction media by filtration. It is also a versatile catalyst for subsequent reactions with several substrates yielding products with the same efficiency even after ten reuses and with minimal leaching. This is the first example of the use of a copper-complexed bridged silsesquioxane for the preparation of a recoverable catalyst in modern Ullmann chemistry. This may represent a promising route to the reduction of waste while maintaining economic viability.
- Benyahya, Sofia,Monnier, Florian,Taillefer, Marc,Man, Michel Wong Chi,Bied, Catherine,Ouazzani, Fouad
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supporting information; scheme or table
p. 2205 - 2208
(2009/10/25)
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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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scheme or table
p. 6037 - 6039
(2009/05/27)
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- Toward optimization of the linker substructure common to transthyretin amyloidogenesis inhibitors using biochemical and structural studies
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To develop potent and highly selective transthyretin (TTR) amyloidogenesis inhibitors, it is useful to systematically optimize the three substructural elements that compose a typical TTR kinetic stabilizer: the two aryl rings and the linker joining them. Herein, we evaluated 40 bisaryl molecules based on 10 unique linker substructures to determine how these linkages influence inhibitor potency and selectivity. These linkers connect one unsubstituted aromatic ring to either a 3,5-X2 or a 3,5-X2-4-OH phenyl substructure (X = Br or CH3). Coconsideration of amyloid inhibition and ex vivo plasma TTR binding selectivity data reveal that direct connection of the two aryls or linkage through nonpolar E-olefin or -CH2CH2- substructures generates the most potent and selective TTR amyloidogenesis inhibitors exhibiting minimal undesirable binding to the thyroid hormone nuclear receptor or the COX-1 enzyme. Five high-resolution TTR·inhibitor crystal structures (1.4-1.8 A?) provide insight into why such linkers afford inhibitors with greater potency and selectivity.
- Johnson, Steven M.,Connelly, Stephen,Wilson, Ian A.,Kelly, Jeffery W.
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supporting information; experimental part
p. 6348 - 6358
(2009/12/03)
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- Nitrogen ligands in copper-catalyzed arylation of phenols: Structure/activity relationships and applications
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In spite of the importance of ligand/ copper-catalyzed arylations of nucleophiles in organic chemistry, the structural and electronic features that make a ligand efficient in these reactions have not been determined until now. In this work, several bident
- Ouali, Armelle,Spindler, Jean-Francis,Jutand, Anny,Taillefer, Marc
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p. 1906 - 1916
(2008/09/17)
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- Significantly improved method for the pd-catalyzed coupling of phenols with aryl halides: Understanding ligand effects
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(Chemical Equation Presented) A variety of diaryl ethers were synthesized by the Pd-catalyzed reaction of (hetero)-aryl halides and phenols. These reactions were achieved through the use of two new di-tert-butylphosphino biaryl ligands that overcome several limitations of previously described methods.
- Burgos, Carlos H.,Barder, Timothy E.,Huang, Xiaohua,Buchwald, Stephen L.
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p. 4321 - 4326
(2007/10/03)
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- 1,1,1-Tris(hydroxymethyl)ethane as a new, efficient, and versatile tripod ligand for copper-catalyzed cross-coupling reactions of aryl iodides with amides, thiols, and phenols
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1,1,1-Tris(hydroxymethyl)ethane was presented as a new, efficient, and versatile tridentate O-donor ligand suitable for the copper-catalyzed formation of C-N, C-S, and C-O bonds. This inexpensive and commercially available tripod ligand has been demonstrated to facilitate the copper-catalyzed cross-coupling reactions of aryl iodides with amides, thiols, and phenols to afford the corresponding desired products in good to excellent yields.
- Chen, Yao-Jung,Chen, Hsin-Hung
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p. 5609 - 5612
(2007/10/03)
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- Mild conditions for copper-catalyzed coupling reaction of phenols and aryl iodides and bromides
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Coupling of phenols and aryl bromides can be efficiently performed by means of catalytic amounts of copper iodide and the inexpensive ligand 1 (structure given in Table 1). The reaction is applicable to a wide range of substrates and proceeds at 60-80 deg;C, the lowest temperatures reported to date for an Ullmann-type synthesis of diaryl ethers. Moreover, the use of aryl bromides and inexpensive K3PO4 as base make this method attractive for applications on an industrial scale.
- Ouali, Armelle,Spindler, Jean-Francis,Cristau, Henri-Jean,Taillefer, Marc
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p. 499 - 505
(2007/10/03)
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- Method of forming a carbon-carbon or carbon-heteroatom linkage
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The invention relates to a method of creating a carbon-carbon or carbon-heteroatom linkage by reacting an unsaturated compound bearing a leaving group and a nucleophilic compound. More specifically, the invention relates to the creation of a carbon-nitrogen linkage involving the arylation of nitrogenous organic derivatives. The inventive method consists in creating a carbon-carbon or carbon-heteroatom linkage by reacting an unsaturated compound bearing a leaving group and a nucleophilic compound providing a carbon atom or a heteroatom (HE) capable of being substituted for the leaving group, thereby creating a C—C or C-HE linkage. The invention is characterised in that the reaction is carried out in the presence of an effective quantity of a catalyst based on copper and at least one ligand comprising at least one imine function and at least one additional nitrogen atom as chelating atoms
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Page/Page column 36
(2010/02/14)
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- Regioselective hypervalent-iodine(III)-mediated dearomatizing phenylation of phenols through direct ligand coupling
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(Chemical Equation Presented) Dearomatization: Treatment of phenols and naphthols substituted at the ortho position by a small electron-donating group D with chlorodiphenyl-λ3-iodane leads to their regioselective ortho phenylation to give cyclohexa-2,4-dienone derivatives (see scheme). The mechanism of this reaction involves a nonradical direct coupling of the ligands.
- Ozanne-Beaudenon, Aurelie,Quideau, Stephane
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p. 7065 - 7069
(2007/10/03)
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- A general and mild Ullmann-type synthesis of diaryl ethers
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(Equation presented) An efficient method for the synthesis of diaryl ethers under particularly mild conditions is described. Inexpensive ligands were found to greatly accelerate the Ullmann-type coupling of aryl bromides or iodides with phenols. A series of diaryl ethers were obtained with excellent yields in acetonitrile in the presence of Cs2CO3 and catalytic copper(I) oxide. The reaction tolerates substrates with unfavorable substitution patterns, such as sterically hindered coupling partners or electron-rich aryl halides.
- Cristau, Henri-Jean,Cellier, Pascal P.,Hamada, Samy,Spindler, Jean-Francis,Taillefer, Marc
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p. 913 - 916
(2007/10/03)
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- Resin-bound triaryl bismuthanes and bismuth diacetates: Novel multidirectional linkers and novel resin-bound arylation reagents
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A general synthesis of resin-bound triaryl bismuthanes and resin-bound triaryl bismuth diacetates starting from commercially available chloromethyl polystyrene is reported. For the first time resin-bound bismuth has been utilized as part of a multidirectional linker system for solid-phase organic synthesis and as a resin-bound arylation reagent.
- Rasmussen, L. Kyhn,Begtrup, Mikael,Ruhland, Thomas
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p. 6890 - 6893
(2007/10/03)
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- Synthesis of diaryl ethers through the copper-catalyzed arylation of phenols with aryl halides using microwave heating
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The copper-catalyzed arylation of phenols with a variety of aryl halides using microwave heating is described.
- He, Huan,Wu, Yong-Jin
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p. 3445 - 3446
(2007/10/03)
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- Process for arylating or vinylating or alkynating a nucleophilic compound
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The present invention concerns a process for arylating or vinylating or alkynating a nucleophilic compound. More particularly, the invention concerns arylating nitrogen-containing organic derivatives. The arylating or vinylating or alkynating process of the invention consists of reacting a nucleophilic compound with a compound carrying a leaving group and is characterized in that the reaction is carried out in the presence of an effective quantity of a catalyst based on a metallic element M selected from groups (VIII), (Ib) and (IIb) of the periodic table and at least one ligand comprising at least one imine function and at least one supplemental nitrogen atom as the chelating atoms.
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- N,N-Dimethyl Glycine-Promoted Ullmann Coupling Reaction of Phenols and Aryl Halides
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(Matrix presented) Ullmann-type diaryl ether synthesis can be performed at 90°C using either aryl iodides or aryl bromides as the substrates under the assistance of N,N-dimethylglycine.
- Ma, Dawei,Cai, Qian
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p. 3799 - 3802
(2007/10/03)
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- Novel electron-rich bulky phosphine ligands facilitate the palladium-catalyzed preparation of diaryl ethers
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A general method for the palladium-catalyzed formation of diaryl ethers is described. Electron-rich, bulky aryldialkylphosphine ligands, in which the two alkyl groups are either tert-butyl or 1-adamantyl, are the key to the success of the transformation. A wide range of electron-deficient, electronically neutral and electron-rich aryl bromides, chlorides, and triflates can be combined with a variety of phenols with the use of sodium hydride or potassium phosphate as base in toluene at 100 °C. The bulky yet basic nature of the phosphine ligand is thought to be responsible for increasing the rate of reductive elimination of the diaryl ether from palladium.
- Aranyos, Attila,Old, David W.,Kiyomori, Ayumu,Wolfe, John P.,Sadighi, Joseph P.,Buchwald, Stephen L.
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p. 4369 - 4378
(2007/10/03)
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