- Synthesis and application of N-heterocyclic carbene-palladium ligands with glycerol dendrons for the Suzuki-Miyaura cross-coupling in water
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Highly active glycerol-dendron-supported N-heterocyclic carbene-palladium catalysts with catalytic sites at the core position were obtained with an efficient modular synthesis. A symmetrical ligand structure was designed to build a larger microenvironment by increasing the number of dendron generations. The catalytic activity was tested in Suzuki-Miyaura cross-coupling reactions. Deprotection of the dendritic supported catalysts allowed the catalytic reaction to take place in neat water, which is highly desirable for a more sustainable processing. A positive dendritic effect was observed for coupling of activated and nonactivated bromoaryls. Georg Thieme Verlag Stuttgart. New York.
- Lukowiak, Maike C.,Meise, Markus,Haag, Rainer
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Read Online
- Suzuki-Miyaura coupling catalyzed by polymer-incarcerated palladium, a highly active, recoverable, and reusable Pd catalyst
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Equation presented. Suzuki-Miyaura coupling using a highly efficient and reusable polymer-incarcerated palladium (Pl Pd) is described. Various coupling reactions proceeded smoothly using Pl Pd with phosphine ligands, and the catalyst could be recovered by simple filtration and reused several times without loss of activity.
- Okamoto, Kuniaki,Akiyama, Ryo,Kobayashi, Shu
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Read Online
- Palladium-catalyzed borylation of aryl bromides and chlorides using phosphatrioxa-adamantane ligands
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Catalysts based on the combination of Pd(OAc)2 and the electron-deficient phosphatrioxa-adamantane ligands are described for borylation of aryl bromides and chlorides. Catalytic evaluation of a small library of phosphatrioxa-adamantane ligands provided some insights on the preferred ligand steric profile for borylation reactions. The corresponding aryl boronate esters were accessed under mild conditions (25–70 °C) and isolated in high yields (up to 96%).
- Lamola, Jairus L.,Moshapo, Paseka T.,Holzapfel, Cedric W.,Christopher Maumela, Munaka
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- Highly Active Fe3O4@SBA-15@NHC-Pd Catalyst for Suzuki–Miyaura Cross-Coupling Reaction
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A novel Pd-NHC functionalized magnetic Fe3O4@SBA-15@NHC-Pd was synthesized and used as an efficient heterogeneous catalyst in the Suzuki–Miyaura C–C bond formation reactions. The Fe3O4@SBA-15@NHC-Pd characterized by X-Ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Fourier Transform Infrared (FTIR) spectroscopy, Scanning Electron Microscopy (SEM), Transmission Electron Microscopy?(TEM), Energy Dispersive X-ray analysis (EDX), Thermogravimetric Analysis (TGA), Differential Thermal Analysis (DTA). The Inductively Coupled Plasma-Optical emission spectroscopy (ICP-OES)?analysis was used to determine the exact amount of Pd (0.33?wt%) in Fe3O4@SBA-15@NHC-Pd. The TEM images of the catalyst showed the existence of palladium nanoparticles immobilized in the catalyst's structure, while no reducing agent was used. The NHC moieties in the catalyst structure could be stabilize Pd(0) nanoparticles prevents agglomeration. The magnetic catalyst was effectively used in the Suzuki–Miyaura cross-coupling reaction of substituted phenylboronic acid derivatives with (hetero)aryl bromides in the presence of a K2CO3 at room temperature in aqueous media and magnetic catalyst could be simply extracted from the reaction mixture by an external magnet. Different aryl bromides were converted to coupled-products in excellent yields with spectacular TOFs values (up to 1,960,339?h?1); in the presence of 1?mg of Fe3O4@SBA-15@NHC-Pd catalyst (contains 3.1 × 10–6?mol% Pd) at room temperature in aqueous media. After reusability experiments, it is found that this catalyst was effectively used up to ten times in the reaction with almost consistent catalytic efficiency. A decrease in the activity of the 10th reused catalyst was found as 9%. Graphic Abstract: [Figure not available: see fulltext.]
- ?zdemir, ?smail,Akko?, Mitat,Alt?n, Serdar,Bu?day, Nesrin,Ya?ar, Sedat
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- Method for preparing biaryl hydrocarbon compound by Suzuki coupling reaction
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The invention discloses a preparation method of a biaryl hydrocarbon compound as shown in a structural formula III (the structural formula and substituent are shown in the specification), which comprises the following steps: adding a nonionic surfactant into a reaction system, and carrying out Suzuki coupling reaction on chlorinated aromatic hydrocarbon as shown in a structural formula I and arylboronic acid as shown in a structural formula II. The preparation method provided by the invention is high in chlorinated aromatic hydrocarbon reaction activity, low in raw material cost, mild in reaction condition, green and environment-friendly.
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Paragraph 0081-0085
(2020/12/30)
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- Method for synthesizing biphenyl compound by taking phenol as raw material
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The invention discloses a method for synthesizing a biphenyl compound by using phenol as a raw material in the technical field of organic chemical synthesis, which comprises the following steps: carrying out a mixed reaction process on phenol or substituted phenol, alkali and 50-90% ethanol aqueous solution, slowly introducing sulfonyl fluoride gas, and carrying out magnetic stirring reaction at normal temperature for 4-12 hours, adding arylboronic acid, alkali and a palladium catalyst into a round-bottom flask, continuing to react for 6-12 hours at normal temperature, after the reaction is finished, adding a saturated edible salt solution into the round-bottom flask, carrying out a water quenching reaction process to obtain a reaction mixture, extracting a reaction product from the reaction mixture by using ethyl acetate, combining organic phases, concentrating filtrate, and separating the concentrated filtrate by using column chromatography to obtain analytically pure biphenyl or terphenyl compounds. By using the method, on one hand, the production cost of the biphenyl compound is reduced, and on the other hand, the method also has a wide application prospect in the aspects of synthesis of natural products, medicines, pesticides, herbicides, polymer conduction materials, liquid crystal materials and the like.
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Paragraph 0062-0064
(2020/07/15)
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- Suzuki-Miyaura coupling catalyzed by a Ni(II) PNP pincer complex: Scope and mechanistic insights
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The nickel(II) pincer complex, [NiCl(PhPNP)] (PhPNP = anion of 2,5-bis(diphenylphosphinomethyl)pyrrole), has been employed as a precatalyst for the Suzuki-Miyaura cross-coupling reaction of aryl halides and boronic acids. Both electron-rich and electron-deficient aromatic bromides were found to undergo coupling with boronic acids in modest yield at elevated temperature in the presence of K3PO4·H2O. Preliminary mechanistic studies of the reaction identified a novel species formulated as the boronate complex, [Ni(OB{OH}{2-tolyl})(PhPNP)], which most likely represents a catalyst deactivation pathway. The productive catalytic cycle was found to be most consistent with a Ni(I)/Ni(III) process where the boronic acid serves as both reductant and nucleophile in the presence of base.
- Madera, Justin,Slattery, Megan,Arman, Hadi D.,Tonzetich, Zachary J.
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- Salicylaldehyde-stabilized palladium nanoparticles for highly efficient suzuki-miyaura reaction at room temperature
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Pd-catalyzed Suzuki-Miyaura cross-coupling reactions promoted by simple and commercial salicylaldehyde-based ligands were investigated. The effect of the ligands was evaluated and the reaction conditions were optimized. Moreover, the physical nature of the palladium was determined by TEM analysis and poison tests. It demonstrated that this catalytic system can be reused for ten consecutive runs and showed excellent activities toward aryl bromides with arylboronic acids at room temperature in air.
- Zhou, Zhen,Cao, Gao,Liu, Ning
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supporting information
p. 547 - 550
(2019/06/11)
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- A new diphosphine-carbonyl complex of ruthenium: an efficient precursor for C-C and C-N bond coupling catalysis
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Reaction of 1,2-bis(diphenylphosphino)benzene (dppbz) with [{Ru(CO)2Cl2}n] affords [Ru(dppbz)(CO)2Cl2], where the two carbonyls are mutually cis and the two chlorides are trans. The molecular structure of [Ru(dppbz)(CO)2Cl2], has been determined by X-ray crystallography, and the stability of the different available stereoisomers has been computationally evaluated. [Ru(dppbz)(CO)2Cl2] has been found to serve as an excellent pre-catalyst for catalytic Suzuki-type C-C coupling and Buchwald-type C-N coupling reactions.
- Mukherjee, Aparajita,Hrovat, David A.,Richmond, Michael G.,Bhattacharya, Samaresh
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p. 10264 - 10272
(2018/08/06)
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- The Highly Efficient Suzuki–Miyaura Cross-Coupling of (Hetero)aryl Chlorides and (Hetero)arylboronic Acids Catalyzed by “Bulky-yet-Flexible” Palladium–PEPPSI Complexes in Air
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A series of Pd–PEPPSI complexes were designed and synthesized. The relationship between catalyst structure and properties was systematically investigated. It was revealed that “bulky-yet-flexible” C3 bearing ancenaphthyl backbone was a highly efficient precatalyst and could be successfully employed in Suzuki–Miyaura reactions of (hetero)aryl chlorides with (hetero)arylboronic acids at a low palladium loading in the presence of a weak inorganic base in air.
- Ouyang, Jia-Sheng,Li, Yan-Fang,Huang, Fei-Dong,Lu, Dong-Dong,Liu, Feng-Shou
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p. 371 - 375
(2017/12/15)
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- Method for preparing biaryl compound by using aryl sulfuryl fluoride as raw material
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The invention discloses a method for preparing a biaryl compound by using aryl sulfuryl fluoride as a raw material. The method comprises the following steps: adding a palladium catalyst, the aryl sulfuryl fluoride, an aryl boride and alkali into a round-bottom flask in sequence; magnetically stirring at a room temperature for carrying out Suzuki cross coupling reaction; after completing the reaction, adding a saturated saline solution for carrying out quenching reaction; extracting a reaction product from a reaction mixture by using ethyl acetate; merging organic phases; concentrating filtrate, and carrying out column chromatography isolation, thus obtaining the analytically pure biaryl compound, wherein the reaction is as shown in a following formula which is shown in the description. Byusing the method disclosed by the invention, on one hand, the production cost of the biaryl compound is reduced, and on the other hand, the method has a wide application prospect in aspects such as natural products, medicines, pesticides, herbicides and synthesis of high polymer conductive materials and liquid crystal materials.
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Paragraph 0056-0057
(2018/06/14)
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- A simple and mild Suzuki reaction protocol using triethylamine as base and solvent
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A simple and mild protocol for the palladium-catalyzed Suzuki reaction of aryl bromides and arylboronic acids is developed. The cross-coupling reactions can be performed at room temperature using 5.0 equiv. of Et3N as solvent and base without any ligands, and affording biaryl products in good yields. In addition, the chemoselecitive Suzuki reaction of bromo-N-methyliminodiacetic acid (MIDA) boronates with arylboronic acids can be achieved in this system, and various unsymmetrical terphenyls have been prepared in moderate yields by one-pot double Suzuki reactions.
- Li, Xinmin,Zhang, Hang,Hu, Qinghong,Jiang, Bo,Zeli, Yuan
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supporting information
p. 3123 - 3132
(2018/12/04)
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- Application of a zwitterionic palladium complex as a metal precursor of recyclable palladium nanoparticles for catalyzing Suzuki-Miyaura coupling reactions
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An efficient recyclable catalyst system for Suzuki-Miyaura coupling reactions in water was developed based on a zwitterionic palladium complex bearing an imidazolium-based carbon donor and tricyclohexylphopshine. The complex served as an effective metal p
- Lee, Jhen-Yi,Tzeng, Ru-Jiun,Wang, Mu-Cheng,Lee, Hon Man
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- Method for preparing biaryl compound under solvent-free condition
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The invention discloses a method for preparing a biaryl compound under a solvent-free condition. The method comprises the following steps: sequentially adding 0.0025-0.005mmol of palladium catalyst, 0.5mmol of aryl halide, 1.0mmol of arylboronic acid and 1.5-2.5mmol of alkali into a round-bottom flask; magnetically stirring at 25 DEG C to perform a Suzuki cross-coupling reaction for 12-24 hours; adding 15mL of saturated saline solution for quenching reaction after the reaction is completed; extracting a reaction product from the reaction mixture with 15mL of ethyl acetate; combining organic phases, concentrating filtrate, and separating with column chromatography to obtain an analytically pure biaryl compound. According to the method, solvent is not required to be added, the pollution problem of organic solvent on the environment can be solved, and the problems of product separation difficulty and difficult surfactant synthesis since water is used as solvent can be avoided. The method has wide application prospect in the fields of synthesis of natural products, medicines, pesticides, herbicide, high-molecular conductive materials and liquid crystal materials.
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Paragraph 0034
(2017/08/30)
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- General copper-catalyzed coupling of alkyl-, aryl-, and alkynylaluminum reagents with organohalides
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We report the first example of a very general Cu-catalyzed cross-coupling of organoaluminum reagents with organohalides. The reactions proceed for the couplings of alkyl-, aryl-, and alkynylaluminum reagents with aryl and heteroaryl halides and vinyl bromides, affording the cross-coupled products in good to excellent yields. Both primary and secondary alkylaluminum reagents can be utilized as organometallic coupling partners. These reactions are not complicated by β-hydride elimination, and as a result rearranged products are not observed with secondary alkylaluminum reagents even for couplings with heteroaryl halides under "ligand-free" conditions. Radical clock experiment with a radical probe and relative reactivity study of Ph3Al with two haloarenes, 1-bromonaphthalene and 4-chlorobenzonitrile, having two different redox potentials indicates that the reaction does not involve free aryl radicals and radical anions as intermediates. These results combined with the result of the Hammett plot obtained by reacting Ph3Al with iodoarenes containing p-H, p-Me, p-F, and p-CF3 substituents, which shows a linear curve (R2 = 0.99) with a ρ value of +1.06, suggest that the current transformation follows an oxidative addition-reductive elimination pathway.
- Shrestha, Bijay,Thapa, Surendra,Gurung, Santosh K.,Pike, Ryan A. S.,Giri, Ramesh
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p. 787 - 802
(2016/02/18)
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- Copper-Catalyzed Negishi Coupling of Diarylzinc Reagents with Aryl Iodides
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We report an efficient copper(I) iodide catalyzed cross-coupling of diarylzinc reagents with aryl iodides. The reaction proceeds under ligand-free conditions at low catalyst loading (5 mol%) and tolerates a variety of functional groups.
- Thapa, Surendra,Vangala, Adarsh S.,Giri, Ramesh
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p. 504 - 511
(2016/02/14)
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- Inherent vs Apparent Chemoselectivity in the Kumada-Corriu Cross-Coupling Reaction
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The Kumada-Corriu reaction is a powerful tool for C-C bond formation, but is seldom utilized due to perceived chemoselectivity issues. Herein, we demonstrate that high-yielding couplings can occur in the presence of many electrophilic and heterocyclic functional groups. Our strategy is mechanically based, matching oxidative addition rates with the rate of syringe pump addition of the Grignard reagent. The mechanistic reason for the effectiveness of this strategy is uncovered by continuous-infusion ESI-MS studies.
- Hua, Xiye,Masson-Makdissi, Jeanne,Sullivan, Ryan J.,Newman, Stephen G.
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supporting information
p. 5312 - 5315
(2016/11/02)
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- The suzuki-miyaura reaction performed using a palladium-n-heterocyclic carbene catalyst and a weak inorganic base
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N-Heterocyclic carbenes (NHCs) have been shown to be useful ligands for the Suzuki-Miyaura cross-coupling at low catalyst loadings. We now report that the commercially available and air-stable [Pd(IPr)(cin)Cl] pre-catalyst permits the formation of various functionalized biaryls from aryl chlorides and boronic acids (37 examples) under very mild conditions using a mixture of ethanol/water as solvent and an inorganic base. [Pd(IPr)(cin)Cl] permits an operationally simple Suzuki-Miyaura reaction under very mild conditions using a mixture of ethanol/water as solvent and an inorganic base.
- Izquierdo, Frédéric,Corpet, Martin,Nolan, Steven P.
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supporting information
p. 1920 - 1924
(2015/03/18)
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- Catalytic Decarboxylative Cross-Coupling of Aryl Chlorides and Benzoates without Activating ortho Substituents
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The restriction of decarboxylative cross-coupling reactions to ortho-substituted or heterocyclic carboxylate substrates was overcome by holistic optimization of a bimetallic Cu/Pd catalyst system. The combination of a CuI/Me4phen decarboxylation catalyst and a [(MeCN)4Pd](OTf)2/XPhos cross-coupling catalyst enables the synthesis of biaryls from inexpensive aryl chlorides and potassium benzoates regardless of their substitution pattern. Lifting the restriction: A combination of a CuI/Me4phen decarboxylation catalyst and a [(MeCN)4Pd](OTf)2/XPhos cross-coupling catalyst enables the synthesis of biaryls from inexpensive aryl chlorides and potassium benzoates regardless of their substitution pattern (see scheme; FG=functional group). This approach lifts the restriction of decarboxylative cross-coupling reactions to ortho-substituted or heterocyclic carboxylate substrates.
- Tang, Jie,Biafora, Agostino,Goossen, Lukas J.
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supporting information
p. 13130 - 13133
(2015/11/02)
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- Pincer-Nickel-Catalyzed Cross-Coupling of Aryl Sulfamates with Arylzinc Chlorides
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The nickel N,N,N-pincer complex 2 was demonstrated to effectively catalyze the cross-coupling of aryl sulfamates with arylzinc chlorides under mild conditions. The reaction is suitable for a wide range of substrates, and tolerates various functional groups. A nickel N,N,N-pincer complex effectively catalyzes the cross-coupling of aryl sulfamates with arylzinc chlorides under mild conditions. The reaction is suitable for a wide range of substrates, and tolerates various functional groups.
- Tao, Jian-Long,Wang, Zhong-Xia
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p. 6534 - 6540
(2015/10/19)
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- Highly Active Bimetallic Nickel-Palladium Alloy Nanoparticle Catalyzed Suzuki-Miyaura Reactions
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A bimetallic Ni-Pd alloy nanoparticle catalyst with a low palladium content (Ni0.90Pd0.10 nanocatalyst) was prepared and its catalytic performance in Suzuki-Miyaura reactions was evaluated along with that of other Ni-Pd nanocatalysts (with varying Ni/Pd molar ratios in the range of ≈0.25-0.75) and the corresponding monometallic, Ni and Pd, analogues. Notably, the bimetallic Ni0.90Pd0.10 alloy nanocatalyst performed exceptionally well for the synthesis of biaryls by employing a wide range of substituted aryl halides and arylboronic acids having electron-donating and electron-withdrawing groups, and they exhibited high recyclability in water/ethanol solution at moderate reaction temperatures. Catalyst poisoning tests and leaching experiments inferred the heterogeneous nature of the Ni0.90Pd0.10 nanocatalysts. The significant synergistic interactions between Ni and Pd account for the observed high catalytic efficacy of the Ni0.90Pd0.10 nanocatalyst. Up, up, and alloy! Highly active bimetallic Ni-Pd alloy nanocatalysts with high Ni/Pd molar ratios facilitate the Suzuki-Miyaura reactions of a wide range of aryl iodides/bromides and arylboronic acids to biaryls in high yields at moderate temperatures in water/ethanol solution. High synergistic interaction between Ni and Pd accounts for the observed high activity and recyclability of the bimetallic Ni-Pd nanocatalysts. FG=functional group.
- Rai, Rohit Kumar,Gupta, Kavita,Behrens, Silke,Li, Jun,Xu, Qiang,Singh, Sanjay Kumar
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p. 1806 - 1812
(2015/06/23)
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- Nickel-Catalyzed Desulfitative Suzuki-Miyaura Cross-Coupling of N,N-Disulfonylmethylamines and Arylboronic Acids
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A nickel-catalyzed approach for the synthesis of biaryl compounds from N,N-disulfonylmethylamines and arylboronic acids has been developed. Instead of arenesulfonyl chlorides, various N,N-disulfonylmethylamines were used as the aryl source through extrusion of SO2 to give cross-coupling products in moderate to good yields. A NiCl2(dppp)-catalyzed [dppp = 1,3-bis(diphenylphosphino)propane] desulfitative Suzuki-Miyaura cross-coupling reaction between N,N-disulfonylmethylamines and arylboronic acids is described for the first time. The biaryl compounds are obtained in moderate to good yields.
- Chen, Liangshun,Lang, Hongyue,Fang, Lei,Yu, Jianjun,Wang, Limin
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p. 6385 - 6389
(2016/02/18)
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- Three-component coupling based on flash chemistry. Carbolithiation of benzyne with functionalized aryllithiums followed by reactions with electrophiles
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A flow microreactor method for three-component coupling of benzyne was developed based on flash chemistry. o-Bromophenyllithium generated from 1-bromo-2-iodobenzene and a functionalized aryllithium generated from the corresponding aryl halide were mixed at -70 °C. In the subsequent reactor o-bromophenyllithium is decomposed to generate benzyne without affecting the functionalized aryllithium at -30 °C, and carbolithiation of benzyne with the aryllithium took place spontaneously. The resulting functionalized biaryllithium was reacted with an electrophile in the subsequent reactor to give the corresponding three-component coupling product. The precise optimization of reaction conditions using the temperature-residence time mapping is responsible for the success of the present transformation. The present method has been successfully applied to the synthesis of boscalid.
- Nagaki, Aiichiro,Ichinari, Daisuke,Yoshida, Jun-Ichi
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supporting information
p. 12245 - 12248
(2014/11/08)
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- Synthesis, characterization and catalytic activity of palladium complexes with α-imino-amidos ligands
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In the present work, a series of steric substituted α-imino-amido palladium complexes, {[Ar-NC(CH3)-C(CH3)(R)-NH-Ar] PdCl2} (C1, R = Me, Ar = 2,6-dimethylphenyl; C2, R = Me, Ar = 2,6-diisopropylphenyl; C3, R = CH2Ph, Ar = 2,6-dimethylphenyl; C4, R = CH2Ph, Ar = 2,6-diisopropylphenyl), were synthesized and characterized. The structures of palladium complexes C3 and C4 were elucidated by X-ray diffraction. These bidentate nitrogen ligands were applied in palladium-catalyzed Suzuki-Miyaura cross-coupling reactions. The effect of ligand substitution as well as reaction conditions on catalytic activity was evaluated. Under the optimization process, the less bulky and electron-donating ligand were successfully used to catalyze the reaction of a variety of aryl bromides and chlorides with arylboronic acids, giving the desired biaryl products in high yields.
- Cao, Gao,Yang, Hai-Qing,Luo, Bao-Tian,Liu, Feng-Shou
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p. 158 - 165
(2013/10/01)
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- Synthesis, characterization, and catalytic activity of nickel(II) alkyl complexes supported by pyrrole-diphosphine ligands
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The organometallic Ni(II) chemistry of the pyrrole-based pincer ligands (P2RPyr)- (P2RPyr = 2,5-(R2PCH2)2C4H2N, R = Ph, Cy) is reported. Reactions of Grignard reagents with [NiCl(P 2RPyr)] afford a variety of alkyl and aryl complexes (methyl, ethyl, benzyl, phenyl, and allyl) that all display square-planar geometries about nickel. The hydride complex [NiH(P2 CyPyr)] can also prepared either through treatment of [NiCl(P 2CyPyr)] with LiHBEt3 or by reaction of H(P2RPyr) with [Ni(COD)2] (COD = 1,4-cyclooctadiene). Reactions of the methyl and hydride complexes with CO and CO2, respectively, evince clean migratory insertion chemistry of the Ni-C and Ni-H bonds. Both the alkyl and chloride complexes are active catalysts for the Kumada coupling of aryl chlorides and aryl or alkyl Grignard reagents at room temperature. The solid-state structures of several of the complexes are reported.
- Venkanna, Gopaladasu T.,Tammineni, Swetha,Arman, Hadi D.,Tonzetich, Zachary J.
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p. 4656 - 4663
(2013/09/23)
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- A ligand-free palladium-catalyzed cross-coupling of aryl sulfinates with aryl bromides
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A ligand-free Pd-catalyzed cross-coupling of aryl sulfinates with aryl bromides has been developed. A variety of aryl bromides and aryl sulfinates undergo this transformation to yield the desired biaryl in a practical and economical manner. Georg Thieme Verlag Stuttgart New York.
- Ortgies, Dirk H.,Forgione, Pat
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p. 1715 - 1721
(2013/09/02)
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- A Palladium Bipyridyl Complex Grafted onto Nanosized MCM-41 as a Heterogeneous Catalyst for Negishi Coupling
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The Negishi coupling of aryl bromides or acyl chlorides with organozinc chlorides catalyzed by a palladium bipyridyl complex anchored on nanosized mobile crystalline material 41 (MCM-41) were investigated. The reactions proceeded smoothly with a very low catalyst loading in THF at 70°C for electron-deficient aryl bromides, which gave good to high yields of the Negishi coupling products. However, reactions in toluene at 110°C were required if electron-rich aryl bromides were employed. For acyl chlorides, the reactions could be performed in THF at 50°C and the corresponding ketones and ynones were obtained in high yields. After centrifugation, it was possible to easily recover the supported catalyst from the reaction mixture, and this could be reused several times without any retreatment or regeneration with only a slight decrease in activity.
- Wu, Wei-Yi,Lin, Tze-Chiao,Takahashi, Tamotsu,Tsai, Fu-Yu,Mou, Chung-Yuan
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p. 1011 - 1019
(2013/05/09)
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- Cross-coupling of ArX with ArMgBr catalyzed by N-heterocyclic carbene-based nickel complexes
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N-Heterocyclic carbene-based pincer nickel complexes were synthesized and characterized. These complexes efficiently catalyze cross-coupling of aryl Grignard reagents with aryl chlorides or fluorides under mild conditions.
- Guo, Wang-Jun,Wang, Zhong-Xia
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p. 1054 - 1061
(2013/04/10)
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- Cross-coupling reaction with lithium methyltriolborate
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We newly developed lithium methyltriolborate as an air-stable white solid that is convenient to handle. The good performance of this triolborate for metal-catalyzed bond-forming reactions was demonstrated in palladium-catalyzed cross-coupling reactions wi
- Yamamoto, Yasunori,Ikizakura, Kazuya,Ito, Hajime,Miyaura, Norio
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p. 430 - 439
(2013/03/13)
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- Palladium mediated C-H bond activation of thiosemicarbazones: Catalytic application of organopalladium complexes in C-C and C-N coupling reactions
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Upon reaction with Pd(PPh3)2Cl2 benzaldehyde thiosemicarbazone undergoes a geometrical change around the imine bond and affords a mixed-ligand complex 1, incorporating an NS-coordinated thiosemicarbazone, a triphenylphosphine and a chloride. Similar reactions with benzophenone thiosemicarbazone and acetophenone thiosemicarbazone proceed without any geometrical change to afford complexes 2 and 3 respectively, containing a CNS-coordinated thiosemicarbazone and a triphenylphosphine. Crystal structures of complexes 1, 2 and 3 have been determined. All the complexes display intense absorptions in the visible region. Catalytic activity of complexes 1, 2 and 3 toward Suzuki type C-C coupling reactions has been examined, and all three are found to efficiently activate all types of C-X bonds (X = I, Br, Cl and even F) and bring about the C-C bond formation with high yield. These complexes are also found to catalyze C-N coupling reactions between aryl halides and primary or secondary amines. While all three complexes are found to be efficient catalysts for both C-C and C-N coupling reactions, complex 2 is found to be a better catalyst than the other two complexes.
- Paul, Piyali,Sengupta, Poulami,Bhattacharya, Samaresh
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supporting information
p. 281 - 288
(2013/04/10)
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- Preparation and application of indolyl secondary phosphine oxides in palladium complexes catalyzed Suzuki-Miyaura cross-coupling reaction
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Several new indolyl secondary phosphine oxides (SPOs), C8H 6N-P(O)(H)(tBu) (4a′), MeC8H 5N-P(O)(H)(tBu) (4b′), and PhC8H 5N-P(O)(H)(tBu) (4c′), were prepared from the reactions of corresponding 1H-indoles with PtBuCl2 and hydrolysis followed. Further reaction of 4a′, a tautomeric form of C 8H6N-P(OH)(tBu) (4a), with Pd(COD)Cl 2 yielded a di-palladium complex, [(4a)(4a-H+)Pd(μ-Cl)] 2 (6a). Crystal structures of PhC8H5N-P(Cl) (tBu) (3c), (4c′) and (6a) were determined by single-crystal X-ray diffraction methods. The stability of this type of SPO is presumably caused by the indolyl scaffold. In addition, SPOs are air- and moisture-stable preligands and are advantageous for the purpose of storage. In this work, these SPO ligands were employed in the Suzuki-Miyaura cross-coupling reactions as catalytic precursors. This catalytic condition has been tolerated to a variety of functional groups and the coupling reactions underwent efficiently with the arylbromides and arylchlorides, respectively.
- Chang, Yen-Yu,Hong, Fung-E
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p. 2327 - 2335
(2013/03/29)
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- Use of dimethyl carbonate as a solvent greatly enhances the biaryl coupling of aryl iodides and organoboron reagents without adding any transition metal catalysts
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The coupling reaction of aryl iodides with arylboronic acids to give biaryl compounds can be efficiently performed without adding a transition metal catalyst. The key to success is the use of dimethyl carbonate as a solvent. This finding provides a new strategy for constructing a biaryl linkage. The Royal Society of Chemistry 2012.
- Inamoto, Kiyofumi,Hasegawa, Chisa,Hiroya, Kou,Kondo, Yoshinori,Osako, Takao,Uozumi, Yasuhiro,Doi, Takayuki
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supporting information; experimental part
p. 2912 - 2914
(2012/03/27)
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- An efficient suzuki-miyaura coupling of aryl sulfamates and boronic acids catalyzed by NiCl2(dppp)
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The Suzuki-Miyaura cross-coupling of aryl sulfamates and boronic acids was investigated by using [1,3-bis(diphenylphosphanyl)propane]nickel(II) chloride {NiCl2(dppp)} as the catalyst. The results showed that NiCl 2(dppp) is a highly active and general catalyst that allows effective Suzuki-Miyaura cross-coupling of aryl sulfamates with a slight excess amount of the boronic acid (1.2 equiv.) in the presence of a low catalyst loading (generally 1.0-1.5 mol-%). The method also displays broad generality not only to various aryl sulfamates, but also to an array of boronic acids. Furthermore, various functional groups are tolerated. These apparent advantages make NiCl2(dppp) a practical and reliable catalyst system for the Suzuki-Miyaura coupling of aryl sulfamates.
- Chen, Guo-Jun,Han, Fu-She
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supporting information; experimental part
p. 3575 - 3579
(2012/07/27)
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- Room-temperature nickel-catalysed cross-couplings of aryl chlorides with arylzincs
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P,N,O-chelate nickel complexes efficiently catalyse the cross-coupling reaction of aryl chlorides with arylzinc reagents in a 11 THF-NMP mixture. The reactions proceed at room temperature with low catalyst loading.
- Liu, Ning,Wang, Li,Wang, Zhong-Xia
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supporting information; scheme or table
p. 1598 - 1600
(2011/03/20)
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- Negishi cross-coupling reaction catalyzed by an aliphatic, phosphine based pincer complex of palladium. biaryl formation via cationic pincer-type Pd IV intermediates
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The aliphatic, phosphine-based pincer complex [(C10H 13-1,3-(CH2P(Cy2)2)Pd(Cl)] (1) is a highly active Negishi catalyst, enable to quantitatively couple various electronically activated, non-activated, deactivated, sterically hindered and functionalized aryl bromides with various diarylzinc reagents within short reaction times and low catalyst loadings. Experimental observations strongly indicate that a molecular mechanism is operative with initial chloride dissociation of 1 and formation of the cationic T-shaped 14e- complex [(C10H13-1,3-(CH2P(C6H 11)2)2)Pd]+ (B), which undergoes oxidative addition of an aryl bromide (Ar′Br) to yield the cationic, penta-coordinated aryl bromide pincer complexes of type [(C10H 13-1,3-(CH2P(Cy2)2)Pd(Br) (aryl′)]+ (C) with the metal center in the oxidation state of +IV and the aryl unit in cis position relative to the aliphatic pincer core. Subsequent transmetalation with Zn(aryl)2 result in the cationic diaryl pincer complexes of type [(C10H13-1,3-(CH 2P(Cy2)2)Pd(aryl)(aryl′)]+ (D), which reductively eliminate the coupling products, thereby regenerating the catalyst. The neutral square planar aryl pincer complex - a possible key intermediate in the catalytic cycle - was found to be reversibly formed in the reaction mixture but is not involved in the catalytic mechanism. Similarly, palladium nanoparticles as the catalytically active form of 1 could have been excluded. The Royal Society of Chemistry 2011.
- Gerber, Roman,Blacque, Olivier,Frech, Christian M.
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experimental part
p. 8996 - 9003
(2011/10/31)
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- Ionically tagged benzimidazole palladium(II) complex: Preparation and catalytic application in cross-coupling reactions
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An imidazolium chloride tagged palladium(II) complex has been conveniently prepared and structurally analyzed. It is active toward cross-coupling of arylboronic acid with aryl halide and benzoyl chloride, giving moderate to high yield of the desired biaryls and aryl ketones, respectively. The present phosphine-free (N-N)Pd(II) complex could be efficiently recycled at least four times with minor decrease of activity in the aqueous Suzuki-Miyaura coupling reaction.
- Zhang, Li,Wu, Junliang,Shi, Lijun,Xia, Chungu,Li, Fuwei
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supporting information; experimental part
p. 3897 - 3901
(2011/08/09)
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- Room temperature palladium-catalyzed cross coupling of aryltrimethylammonium triflates with aryl grignard reagents
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Figure Presented. Aryltrimethylammonium triflates and tetrafluoroborates were found to be highly reactive electrophiles in the Pd-catalyzed cross coupling with aryl Grignard reagents. The coupling reactions proceed at ambient temperature with a nearly stoichiometric quantity of Grignard reagent, and diverse functionality is tolerated. Competition experiments established the reactivity of PhNMe3OTf relative to PhCl, PhBr, PhI, and PhOTf.
- Reeves, Jonathan T.,Fandrick, Daniel R.,Tan, Zhulin,Song, Jinhua J.,Lee, Heewon,Yee, Nathan K.,Senanayake, Chris H.
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supporting information; experimental part
p. 4388 - 4391
(2010/11/17)
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- [Pd(Cl)2(P(NC5H10)(C6H 11)2)2] - A highly effective and extremely versatile palladium-based negishi catalyst that efficiently and reliably operates at low catalyst loadings
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[Pd(Cl)2(P(NC5H10)-(C6H 11)2]2] (1) has been prepared in quantitative yield by reacting commercially available [Pd(cod)(Cl)2] (cod = cyclooctadiene) with readily prepared 1-(dicyclohexylphosphanyl)piperidine in toluene under N2 within a few minutes at room temperature. Complex 1 has proved to be an excellent Negishi catalyst, capable of quantitatively coupling a wide variety of electronically activated, non-activated, deactivated, sterically hindered, heterocyclic, and functionalized aryl bromides with various (also heterocyclic) arylzinc reagents, typically within a few minutes at 100°C in the presence of just 0.01 mol% of catalyst. Aryl bromides containing nitro, nitrile, ether, ester, hydroxy, carbonyl, and carboxyl groups, as well as acetais, lactones, amides, anilines, alkenes, carboxylic acids, acetic acids, and pyridines and pyrimidines, have been successfully used as coupling partners. Furthermore, electronic and steric variations are tolerated in both reaction partners. Experimental observations strongly indicate that a molecular mechanism is operative.
- Bolliger, Jeanne L.,Frech, Christian M.
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experimental part
p. 11072 - 11081
(2010/11/16)
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- Suzuki-Miyaura cross-coupling catalyzed by protein-stabilized palladium nanoparticles under aerobic conditions in water: Application to a one-pot chemoenzymatic enantioselective synthesis of chiral biaryl alcohols
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The preparation of palladium nanoparticles stabilized primarily within the protein cavity of a highly thermostable Dps protein (DNA binding protein from starved cells) and the use of this precatalyst system in Suzuki-Miyaura cross-coupling reactions under
- Prastaro,Ceci,Chiancone,Boffi,Cirilli,Colone,Fabrizi,Stringaro,Cacchi
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scheme or table
p. 1929 - 1932
(2010/06/15)
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- N-heterocyclic carbene derived Nickel-Pincer complexes: Efficient and applicable catalysts for Suzuki-Miyaura coupling reactions of aryl/alkenyl tosylates and mesylates
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Catalytic activities of NHC-derived nickel-pincer complexes for the Suzuki-Miyaura coupling reactions of aryl/alkenyl to- sylates and mesylates are described. In the presence of a catalytic amount of nickelacycle 1a, a wide array of tosylates and mesylates reacted with several aryl- and alkenylboronic acids to afford the coupling products, generally in high yields. Fine tuning of the reaction conditions for each class of electrophiles was achieved only by choosing the appropriate reaction medium (DME for tosylates, dioxane for mesylates).
- Kuroda, Jun-Ichi,Inamoto, Kiyofumi,Hiroya, Kou,Doi, Takayuki
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experimental part
p. 2251 - 2261
(2009/08/09)
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- BICYCLIC MONOPHOSPHINES
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A compound of formula (I): wherein: RP1 and RP2 are independently selected from C3-12 alkyl groups; RC is a C5-6 aryl group, optionally substituted by one or more groups selected from: C1-7 alkyl, C1-7 alkoxy, halo, NH2, C1-7alkylamino, di-C1-7alkylamino, and C5-6 aryl; RA1 and RA2 are independently selected from H, Cl, and an optionally substituted group selected from: C1-7 alkyl, C1-7 alkoxy, C1-7 alkylthio and C5-6 aryl, wherein the optional substituents are selected from: C1-7 alkyl, C1-7 alkoxy, halo, NH2, C1-7alkylamino, di-C1-7alkylamino, and C5-6 aryl.
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Page/Page column 22-23
(2009/12/23)
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- New electrochemlcally generated polymeric pd complexes as heterogeneous catalysts for Suzuki cross-coupling reactions
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Electrochemically generated films of polymerized (diaminooligothiophene) palladium complexes as heterogeneous catalysts for Suzuki cross-coupling reactions are reported. The electrodeposition of these polymeric species onto porous graphite electrodes allows for easy removal of the organo-metallic species from the reaction mixture and convenient reuse in subsequent (up to 6) reactions.
- Bandini, Marco,Pietrangelo, Agostino,Sinisi, Riccardo,Umani-Ronchi, Achille,Wolf, Michael O.
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supporting information; experimental part
p. 3554 - 3561
(2009/12/01)
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- Efficient Negishi coupling reactions of aryl chlorides catalyzed by binuclear and mononuclear nickel-N-heterocyclic carbene complexes
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(Chemical Equation Presented) We describe the first nickel-N-heterocyclic carbene catalyzed Negishi cross-coupling reaction of a variety of unactivated aryl chlorides, heterocyclic chlorides, aryl dichlorides, and vinyl chloride. The mononuclear and binuclear nickel-NHC complexes supported by heteroarene-functionalized NHC ligands are found to be highly efficient for the coupling of unactivated aryl chlorides and organozinc reagents, leading to biaryls and terphenyls in good to excellent yields under mild conditions. For all aryl chlorides, the binuclear nickel catalysts show activities higher than those of mononuclear nickel complexes because of possible bimetallic cooperative effect.
- Xi, Zhenxing,Zhou, Yongbo,Chen, Wanzhi
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experimental part
p. 8497 - 8501
(2009/04/04)
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- One-pot synthesis of carbazole via tandem Suzuki-Miyaura and amination reaction
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One-pot synthesis of carbazole from two aromatic rings was accomplished by a tandem Suzuki-Miyaura and amination reaction. Our novel phosphine ligand for both reactions efficiently mediates a sequential intermolecular biaryl formation and ring-closing amination. Georg Thieme Verlag Stuttgart.
- Kitamura, Yuki,Yoshikawa, Seiji,Furuta, Takumi,Kan, Toshiyuki
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p. 377 - 380
(2008/04/01)
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- N-heterocyclic benzhydrylamines as new N,N-bidentate ligands in palladium complexes: Synthesis, characterization and catalytic activity
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The synthesis of new N,N-bidentate ligands based on a π-deficient N-heterocyclic benzhydrylamine core is described. The corresponding air-stable palladium complexes are obtained in high yields and fully characterized by NMR spectroscopy and X-ray structur
- Terrasson, Vincent,Prim, Damien,Marrot, Jerome
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scheme or table
p. 2739 - 2745
(2009/03/12)
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- Electron-rich, bicyclic biaryl-like KITPHOS monophosphines via [4+2] cycloaddition between 1-alkynylphosphine oxides and anthracene: Highly efficient ligands for palladium-catalysed C-N and C-C bond formation
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Electron-rich, bicyclic biaryl-like KITPHOS monophosphines have been prepared via Diels-Alder cycloaddition between 1-alkynylphosphine oxides and anthracene in an operationally straightforward and highly modular synthetic protocol that will allow access to an architecturally and electronically diverse family of ligands. Palladium complexes of these ligands are highly efficient catalysts for the Buchwald-Hartwig amination and Suzuki-Miyaura coupling of a wide range of aryl chlorides, which for the vast majority of substrate combinations outperform their o-(dicyclohexylphosphino) biphenyl-based counterparts.
- Doherty, Simon,Knight, Julian G.,Smyth, Catherine H.,Jorgenson, Graeme A.
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supporting information; experimental part
p. 1801 - 1806
(2009/07/25)
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- Palladium on carbon as a precatalyst for the Suzuki-Miyuara cross-coupling of aryl chlorides
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Palladium on carbon is used as a precatalyst for Suzuki-Miyaura reaction of aryl chlorides and aryl boronic acids. An efficient catalyst system is obtained that allows the reaction of substrates that are difficult to couple under ligand free conditions. This includes electron rich and sterically hindered aryl chlorides as well as electron deficient and sterically hindered boronic acids. We have discovered that the amount of ligand needed to catalyze these reactions can be significantly decreased by incorporating an incubation period. This study also provides valuable insight into the mechanism of the Pd/C-catalyzed Suzuki-Miyaura cross-coupling. For example, mercury poisoning studies provide evidence that the active catalytic species is homogeneous. However, catalyst reuse and low metal contamination indicate that this system retains many of the advantages of a heterogeneous catalyst. From these results, a catalytic cycle is proposed.
- Simeone, Joseph P.,Sowa Jr., John R.
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p. 12646 - 12654
(2008/03/17)
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- Synthesis and characterization of R2PN=P(iBuNCH 2CH2)3N: A new bulky electron-rich phosphine for efficient Pd-assisted Suzuki-Miyaura cross-coupling reactions
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(Chemical Equation Presented) Pro-azaphosphatrane 1a [P( 1BuNCH2CH2)3N] reacts with iodine under mild conditions to give [IP-(iBuNCH2CH 2)3N]I in excellent yield, which on subsequent reaction with ammonia followed by deprotonation with KOtBu provided HN=P( iBuNCH2CH2)3N (3a) in quantitative yield. Reaction of 3a with R′2PCl afforded sterically bulky electron-rich phosphines of the type R′2PN=P( iBuNCH2CH2)3N (4) [R′ = Ph (4a), iPr (4b), tBu (4c)]. The Pd(OAc)2/4c catalyst system was particularly efficient for the coupling of arylboronic acids with aryl bromides as well as aryl chlorides to give biaryls in excellent yields.
- Kingston, Jesudoss V.,Verkade, John G.
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p. 2816 - 2822
(2008/02/01)
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- An efficient catalyst system for palladium(0)-catalyzed cross-coupling of aryltrialkoxysilanes with aryl halides
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A combination of Pd(dba)2 and a bisphosphine ligand, bis(2-diisopropylphosphinophenyl)ether, has proven to be general and efficient in fluoride-induced cross-coupling of aryltrialkoxysilanes with aryl halides. The substrate scope is broad and includes a variety of aryl bromides and chlorides. Georg Thieme Verlag Stuttgart.
- Murata, Miki,Yoshida, Syo,Nirei, Shin-Ichiro,Watanabe, Shinji,Masuda, Yuzuru
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p. 118 - 120
(2007/10/03)
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- Novel polymer incarcerated palladium with phosphinated polymers: Active catalyst for Suzuki-Miyaura coupling without external phosphines
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(Chemical Equation Presented) Immobilization of a palladium catalyst with use of new phosphinated polymers was carried out utilizing the polymer incarcerated (PI) method. This phosphinated PI Pd catalyst showed excellent activity in Suzuki-Miyaura couplin
- Nishio, Ryo,Sugiura, Masaharu,Kobayashi, Shu
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p. 4831 - 4834
(2007/10/03)
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