- 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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- 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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- 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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- On the frontier between nucleophilic aromatic substitution and catalysis
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A study on the arylation of heteroatom nucleophiles by using activated haloarenes, with or without metal catalysts, is reported. A discussion concerning the involvement of traces of metals is presented, supported by an unexpected ''ligand'' effect in the absence of added metal catalysts. We believe that the frontier between nucleophilic aromatic substitution and catalysis will likely prove to be much harder to delimit than is generally thought. S NAr or catalysis? A study on the arylation of heteroatom nucleophiles by using activated haloarenes, with or without added metal catalysts, is reported. A discussion concerning the involvement of traces of metals is presented, supported by an unexpected "ligand" effect in the absence of added metal catalysts (see scheme, EWG=electron-withdrawing group).
- Pichette Drapeau, Martin,Ollevier, Thierry,Taillefer, Marc
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supporting information
p. 5231 - 5236
(2014/05/20)
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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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Page/Page column 13
(2012/01/03)
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- Selective one-pot access to symmetrical or unsymmetrical diaryl ethers by copper-catalyzed double arylation of a simple oxygen source
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Great CO-mbination: A novel method is reported for the controlled one-pot synthesis of various symmetrical or unsymmetrical diaryl ethers by double arylation of a simple inorganic oxygen source (see scheme). This versatile and highly selective process is based on the use of a cheap and low toxicity copper catalytic system.
- Tlili, Anis,Monnier, Florian,Taillefer, Marc
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supporting information; experimental part
p. 12299 - 12302
(2011/02/16)
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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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- POLY-N-HETEROCYCLIC CARBENE TRANSITION METAL COMPLEXES AND N-HETEROCYCLIC CARBENE TRANSITION METAL COMPLEXES FOR CARBON-SULFUR AND CARBON-OXYGEN COUPLING REACTIONS
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Methods for carbon-sulfur (C S) or carbon-oxygen (C-O) coupling reactions are provided. The methods involve the use of a transition metal complex comprising a heterocyclic carbene ligand complexed with a transition metal. Transition metal complexes comprising a heterocyclic carbene ligand complexed with nickel are also provided. The nickel heterocylic carbene complexes may be used for C-S or C-O coupling reactions.
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Page/Page column 35-36
(2009/01/20)
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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; experimental part
p. 6037 - 6039
(2009/05/27)
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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; experimental part
p. 2205 - 2208
(2009/10/25)
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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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- 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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