- Cost-effective bio-derived mesoporous carbon nanoparticles-supported palladium catalyst for nitroarene reduction and Suzuki–Miyaura coupling by microwave approach
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A new heterogeneous catalyst was synthesized by immobilizing Pd on areca nut kernel-derived carbon nanospheres (CNSs). The CNSs, without any further activation processes, accommodated 3% of Pd on their surface. The new Pd/CNS material was used for the reduction of nitroarenes and Suzuki–Miyaura coupling of bromoarenes with aryl boronic acids. The reactions were conducted under microwave irradiation at 160 °C using 12 mol% of Pd/CNS (0.36% actual Pd content). The reduction of nitroarenes into their respective amino compounds was achieved in 10–20 min (conversion up to 100%); by contrast, the Suzuki–Miyaura reactions yielded up to 98% at 150 °C with 10 mol% of Pd/CNS catalyst. The products were identified using gas chromatography and nuclear magnetic resonance spectroscopy. The catalyst was isolated from reaction mixture and reused without any significant loss in the activity. Thus, the present work introduces one-pot-derived porous CNSs as efficient catalytic support to Pd, establishing an alternative to existing Pd/C in terms of cost and efficiency.
- Supriya,Ananthnag, Guddekoppa S.,Shetti, Vijayendra S.,Nagaraja,Hegde, Gurumurthy
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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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- Palladium-catalyzed, ligand-free Suzuki reaction in water using aryl fluorosulfates
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Aryl fluorosulfates were prepared by a simple method and employed as coupling partners in the Suzuki-Miyaura reaction. The cross-coupling reactions were performed in water under air at room temperature without ligands or additives such as surfactants or phase-transfer reagents and proceeded smoothly to give excellent yields. Aryl fluorosulfates could also be used as alternatives to halides or triflates in other coupling reactions.
- Liang, Qiaobin,Xing, Ping,Huang, Zuogang,Dong, Jiajia,Sharpless, K. Barry,Li, Xiaoxian,Jiang, Biao
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- An efficient Pd(II)-(2-aminonicotinaldehyde) complex as complementary catalyst for the Suzuki-Miyaura coupling in water
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An efficient new Pd(II)-(2-aminonicotinaldehyde)-catalyzed Suzuki-Miyaura coupling of the aryl halides (Br, Cl and I) and organoboronic acids at moderate temperature in water is described. Low catalyst loading, easy accessibility, being an air-stable catalyst, functional group compatibility, and water as the reaction medium are some of the key features of this synthetic method. This protocol is also applicable for gram scale.
- Thunga, Sanjeeva,Poshala, Soumya,Anugu, Naveenkumar,Konakanchi, Ramaiah,Vanaparthi, Satheesh,Kokatla, Hari Prasad
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- Suzuki–Miyaura Coupling of (Hetero)Aryl Sulfones: Complementary Reactivity Enables Iterative Polyaryl Synthesis
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Ideal organic syntheses involve the rapid construction of C?C bonds, with minimal use of functional group interconversions. The Suzuki–Miyaura cross-coupling (SMC) is a powerful way to form biaryl linkages, but the relatively similar reactivity of electrophilic partners makes iterative syntheses involving more than two sequential coupling events difficult to achieve without additional manipulations. Here we introduce (hetero)aryl sulfones as electrophilic coupling partners for the SMC reaction, which display an intermediate reactivity between those of typical aryl (pseudo)halides and nitroarenes. The new complementary reactivity allows for rapid sequential cross-coupling of arenes bearing chloride, sulfone and nitro leaving groups, affording non-symmetric ter- and quateraryls in only 2 or 3 steps, respectively. The SMC reactivity of (hetero)aryl sulfones is demonstrated in over 30 examples. Mechanistic experiments and DFT calculations are consistent with oxidative addition into the sulfone C?S bond as the turnover-limiting step. The further development of electrophilic cross-coupling partners with complementary reactivity may open new possibilities for divergent iterative synthesis starting from small pools of polyfunctionalized arenes.
- Chatelain, Paul,Sau, Abhijit,Rowley, Christopher N.,Moran, Joseph
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- An efficient and simple protocol for a PdCl2-ligandless and additive-free Suzuki coupling reaction of aryl bromides
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A highly efficient, convenient, and environmentally friendly protocol was developed for the PdCl2-catalyzed ligandless and additive-free Suzuki reaction of aryl bromides with arylboronic acids in water/ethanol.
- Qiu, Jun,Wang, Limin,Liu, Mingtao,Shen, Qiang,Tang, Jun
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- Pd-nanoparticles catalyzed denitrogenative coupling of aryl halides with arylhydrazines: Greener approach for biaryls synthesis under ligand-free condition
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The greener approach for the synthesis of biaryl using palladium nanoparticle (Pd–NPs) catalyzed denitrogenative coupling between aryl hydrazine and aryl halides under ligand-free condition has been described. The phytochemicals of the black pepper extract plays a dual role in reduction of PdII to Pd0 and acts as stabilizing agent for Pd–NPs. The electronically diver's arylhydrazines and commercially available aryl halides are used for the synthesis of symmetrical and unsymmetrical biaryls in good to excellent yield. The mechanism is well supported by control experiment and the recyclability, turnover number and turnover frequency of biogenically synthesized Pd–NPs is studied.
- Hegde, Rajeev V.,Ghosh, Arnab,Patil, Siddappa A.,Dateer, Ramesh B.
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- N-Methylimidazole functionalized carboxymethycellulose-supported Pd catalyst and its applications in Suzuki cross-coupling reaction
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In this paper, N-Methylimidazole functionalized carboxymethylcellulose-supported palladium nanoparticles (CMC-NHC-Pd) was synthesized and characterized by TEM, SEM, EDX, CP/MAS 13C NMR, FT-IR, TGA, XRD, and XPS analysis. The prepared nanoparticles can be used as an environmentally-friendly and trifunctional catalyst. The well-designed CMC supported palladium nanoparticles catalyst with polydentate ligands is also stable and efficient for Suzuki cross-coupling reactions under mild conditions through the cooperative interaction of trifunctional capturing sites with palladium, ?COO?, ?OH and N-Methylimidazole. This catalyst can be readily recovered by a few cycles of simple filtration. This work proposes a plausible trifunctional catalyst complex.
- Dong, Yahao,Wu, Xiaotian,Chen, Xiaofeng,Wei, Yuping
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- Microwave enhanced ligand- and base-free cross-coupling of potassium aryltrifluoroborates salts with aryl triflates
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A microwave enhanced ligand- and base-free protocol for the cross-coupling of potassium aryltrifluoroborate salts with triflates is reported.
- Kabalka, George W.,Zhou, Li-Li,Naravane, Abhijit
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- Cellulose-supported N-heterocyclic carbene-palladium catalyst: Synthesis and its applications in the Suzuki cross-coupling reaction
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A cellulose-supported N-methylimidazole-palladium catalyst (Cell-NHC-Pd) was synthesized and used for Suzuki cross-coupling reactions between aryl halides and phenylboronic acids to create the corresponding coupling products in good to excellent yields. Moreover, the catalyst is easily recovered using only a few cycles of simple filtration.
- Wang, Xiaoxia,Hu, Peibo,Xue, Fengjun,Wei, Yuping
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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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- Use of polymer-supported Pd reagents for rapid and efficient Suzuki reactions using microwave heating
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A rapid and efficient Suzuki coupling protocol has been developed utilizing polymer-supported palladium catalysts and microwave irradiation. It is also shown that solid-phase extraction of excess boronic acids can be rapidly and conveniently accomplished by utilization of a silica-supported carbonate base.
- Wang, Ying,Sauer, Daryl R.
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- Palladium nanoparticle supported on nitrogen-doped porous carbon: Investigation of structural properties and catalytic activity on Suzuki–Miyaura reactions
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Novel palladium-doped nanoporous carbon composite material obtained via thermolysis of amorphous zeolitic imidazolate framework (aZIF) was synthesized and used as an efficient catalyst on Suzuki–Miyaura cross-coupling reactions of aryl bromides. With this developed catalytic system, the Suzuki–Miyaura cross-coupling reaction was accomplished in aqueous solutions, and biaryls were obtained in good to excellent yields in a short reaction time. The APC-750@Pd catalyst was characterized by Fourier Transform Infrared spectroscopy (FTIR), X-ray Diffraction (XRD), Scanning Electron Eicroscopy (SEM), X-ray Photoelectron Spectroscopy (XPS), Transmission Electron Microscopy (TEM), Thermal Gravimetric Analysis (TGA), Differential Thermal Analysis (DTA), Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and Brunauer–Emmett–Teller (BET) analysis tecniques. N-doped porous carbon material (NPC-1000) was synthesized by thermolysis from aZIF. Activated porous carbon material (APC-750) was fabricated via fused at 750°C with KOH from NPC-1000. The APC-750@Pd was obtained as a result of the interaction of APC-750 and PdCl2 in deionized water. The cross-coupling reaction of different aryl bromides with phenylboronic acid was investigated to show the potential of the APC-750@Pd in the Suzuki–Miyaura cross-coupling reactions. The APC-750@Pd catalyst could be recycled at least five times with a 15% loss of catalytic efficiency in this catalytic system.
- Bu?day, Nesrin,Alt?n, Serdar,Ya?ar, Sedat
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- Manganese-Catalyzed Aerobic Heterocoupling of Aryl Grignard Reagents
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An improved protocol has been developed for the MnCl2-catalyzed cross-coupling reaction of two arylmagnesium bromides under dioxygen. The reaction was achieved by using the Grignard reagents in a 2:1 ratio and 20 % of MnCl2. Very good yields of the heterocoupling product were obtained when the limiting Grignard reagent underwent little homocoupling under the reaction conditions. Arylmagnesium bromides that contain p-methoxy, p-(dimethylamino), p-fluoro, and p-chloro substituents were shown to afford high product yields in the cross-coupling reactions with a variety of substituted aryl Grignard reagents. Heterocyclic Grignard reagents, on the other hand, were less effective substrates for this transformation because of the rapid homocoupling of these reagents under the reaction conditions.
- Ghaleshahi, Hajar Golshahi,Antonacci, Giuseppe,Madsen, Robert
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- Palladium-catalyzed Suzuki-Miyaura cross-couplings of aryl tosylates with potassium aryltrifluoroborates
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(Chemical Equation Presented) Pd-catalyzed Suzuki-Miyaura cross-coupling reaction of aryl tosylates with potassium aryl trifluoroborate in the presence of bulky and electron-rich phosphine ligand is described. In addition, a useful chemoselective coupling of an aryl chloride in the presence of a tosyloxy group was demonstrated.
- Zhang, Liang,Meng, Tianhao,Wu, Jie
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- Palladium-catalyzed ligand-free and efficient Suzuki-Miyaura reaction of N-methyliminodiacetic acid boronates in water
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A green and efficient protocol has been developed for the Pd(OAc)2-catalyzed ligand-free Suzuki-Miyaura reaction of N-methyliminodiacetic acid (MIDA) boronates in water. In the presence of Pd(OAc)2 as a catalyst and (i-Pr)2NH as a base, the cross-coupling reactions of aryl bromides with aryl MIDA boronates proceeded smoothly in water without any surfactant, and various functional groups were tolerated under the optimized conditions.
- Liu, Chun,Li, Xinmin,Wang, Xinnan,Qiu, Jieshan
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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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- Nickel- and Palladium-Catalyzed Cross-Coupling of Stibines with Organic Halides: Site-Selective Sequential Reactions with Polyhalogenated Arenes
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Herein, we disclose a general and efficient method for the synthesis of Sb-aryl and Sb-alkyl stibines by the nickel-catalyzed cross-coupling of halostibines with organic halides. The synthesized Sb-aryl stibines couple with aryl halides to give biaryls efficiently via palladium catalysis. Sequential reactions of stibines with polyhalogenated arenes bearing active C–I/C–Br sites and inactive C–Cl sites successfully proceeded, resulting in the formation of a variety of complex molecules with good site selectivity. Drugs such as diflunisal and fenbufen, as well as a fenofibrate derivative, were synthesized on gram scales in good yields, together with the high recovery of chlorostibine. Furthermore, catalytic mechanisms are proposed based on the results of control experiments.
- Ghaderi, Arash,Kambe, Nobuaki,Le, Liyuan,Lu, Hao,Qiu, Renhua,Tang, Ting,Tong, Zhou,Wong, Wai-Yeung,Xu, Zhi,Yin, Shuang-Feng,Zeng, Dishu,Zhang, Dejiang,Zhang, Zhao
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p. 854 - 867
(2022/01/19)
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- Photocatalyzed Transition-Metal-Free Oxidative Cross-Coupling Reactions of Tetraorganoborates**
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Readily accessible tetraorganoborate salts undergo selective coupling reactions under blue light irradiation in the presence of catalytic amounts of transition-metal-free acridinium photocatalysts to furnish unsymmetrical biaryls, heterobiaryls and arylated olefins. This represents an interesting conceptual approach to forge C?C bonds between aryl, heteroaryl and alkenyl groups under smooth photochemical conditions. Computational studies were conducted to investigate the mechanism of the transformation.
- Music, Arif,Baumann, Andreas N.,Boser, Florian,Müller, Nicolas,Matz, Florian,Jagau, Thomas C.,Didier, Dorian
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supporting information
p. 4322 - 4326
(2021/02/11)
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- Potassium trimethylsilanolate enables rapid, homogeneous suzuki-miyaura cross-coupling of boronic esters
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Herein, a mild and operationally simple method for the Suzuki-Miyaura cross-coupling of boronic esters is described. Central to this advance is the use of the organic-soluble base, potassium trimethylsilanolate, which allows for a homogeneous, anhydrous cross-coupling. The coupling proceeds at a rapid rate, often furnishing products in quantitative yield in less than 5 min. By applying this method, a >10-fold decrease in reaction time was observed for three published reactions which required >48 h to reach satisfactory conversion.
- Delaney, Connor P.,Kassel, Vincent M.,Denmark, Scott E.
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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 0077-0079; 0089-0091
(2020/07/15)
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- Method for synthesizing biphenyl compound by taking suaeda salsa extract liquor as solvent
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The invention discloses a method for synthesizing a biphenyl compound by using suaeda salsa extract as a solvent in the technical field of organic chemical synthesis, which comprises the following steps: roasting suaeda salsa in a muffle furnace to obtain ash, dissolving the ash in distilled water, refluxing, cooling the solution, and filtering to obtain a faint yellow solution which is the suaedasalsa extract liquor; sequentially adding 1mmol of aryl halide, 1.1mmol of arylboronic acid, 0.001mmol to 0.01mmol of a catalyst and 4ml of the suaeda salsa extract liquor into a round-bottom flask,stirring at 100 DEG C to react for 2 hours, cooling the reactant to room temperature, filtering, mixing the obtained filter residue with a palladium catalyst to obtain a mixture; and dissolving the mixture in ethyl acetate, filtering to remove the palladium catalyst, and drying the filtrate by distillation to obtain the biphenyl compound. According to the scheme, a phosphine ligand, alkali and anadditive do not need to be added, a Suzuki reaction system with biomass extract as a reaction medium is adopted, and a green, simple, convenient and efficient method is provided for synthesizing biphenyl compounds.
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Paragraph 0063-0064
(2020/06/30)
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- Ferrocenyl palladacycles derived from unsymmetrical pincer-type ligands: Evidence of Pd(0) nanoparticle generation during the Suzuki-Miyaura reaction and applications in the direct arylation of thiazoles and isoxazoles
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A new family of ferrocenyl-palladacycle complexes Pd(L1)Cl (Pd1) and Pd(L2)Cl (Pd2) were synthesized and characterized by UV-visible, IR, ESI-MS, and NMR spectral studies. The molecular structures of Pd1 and Pd2 were determined by X-ray crystallographic studies. Palladacycle catalyzed Suzuki-Miyaura cross-coupling reactions were investigated utilizing the derivatives of phenylboronic acids and substituted chlorobenzenes. Mechanistic investigation authenticated the generation of Pd(0) nanoparticles during the catalytic cycle and the nanoparticles were characterized by XPS, SEM and TEM analysis. Direct C-H arylation of thiazole and isoxazole derivatives employing these ferrocenyl-palladacycle complexes was examined. The reaction model for the arylation reaction implicating the in situ generation of Pd(0) nanoparticles was proposed.
- Maji, Ankur,Singh, Anshu,Mohanty, Aurobinda,Maji, Pradip K.,Ghosh, Kaushik
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supporting information
p. 17083 - 17096
(2019/11/26)
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- Preparing method of aromatic nitrile or alkenyl nitrile compound
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The invention discloses a preparing method of an aromatic nitrile or alkenyl nitrile compound. The preparing method comprises the following step that under protection of inert gas, an aryl or heteroaryl sulphonate compound shown in a formula II or an alkenyl sulphonate compound shown in a formula IV and a cyanation reagent are subjected to a cross-coupling reaction as is shown below in a solvent under the condition of the presence of a nickel complex, metal zinc and an additive to obtain the aromatic nitrile or alkenyl nitrile compound, wherein 4-dimethylamiopryidine (DMAP) is adopted as the additive, and zinc cyanide is adopted as the cyanation reagent. By means of the preparing method, cyanation of aryl sulphonate, heteroaryl sulphonate or alkenyl sulphonate can be simply and efficientlyachieved with a cheap catalysis system; moreover, the functional group compatibility and substrate universality are good, and a better application prospect and higher using value are provided for achieving industrial synthesis of the aromatic nitrile or alkenyl nitrile compound.
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Paragraph 0130-0132; 0193-0195; 0232-0233
(2019/10/01)
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- Facile and efficient protocols for C–C and C–N bond formation reactions using a superparamagnetic palladium complex as reusable catalyst
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Abstract: Facile and efficient protocols for some multicomponent coupling reactions such as the Suzuki reaction and synthesis of polyhydroquinoline and 2,3-dihydroquinazoline-4-(1H)-one derivatives using a superparamagnetic palladium complex as catalyst have been developed. Graphical abstract: [Figure not available: see fulltext.].
- Karimi Zarchi, Mohammad Ali,Darbandizadeh Mohammad Abadi, Seyed Shahab Addin
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p. 2605 - 2639
(2019/02/13)
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- Ligand-free palladium catalyzed Ullmann biaryl synthesis: 'Household' reagents and mild reaction conditions
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A palladium catalysed Ullmann biaryl synthesis has been developed using hydrazine hydrate as the reducing reagent at room temperature. The combination of Pd(OAc)2 and hydrazine hydrate works smoothly for the coupling of both electron-rich and electron-deficient aryl iodides, as well as hetero-aryl iodides, leading to a wide range of biaryls in good to excellent yields. The reaction requires only 1 mol% Pd(OAc)2 and the in situ generated palladium naoparticles are found to be active catalysts.
- Gong, Xinchi,Wu, Jie,Meng, Yunge,Zhang, Yulan,Ye, Long-Wu,Zhu, Chunyin
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supporting information
p. 995 - 999
(2019/03/12)
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- Nickel-Catalyzed Cyanation of Phenol Derivatives with Zn(CN)2 Involving C-O Bond Cleavage
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An efficient nickel-catalyzed cyanation of aryl sulfonates, fluorosulfonates, and sulfamates with Zn(CN)2 was developed, which provides a facile access to the nitrile products in generally good to excellent yields. The reaction is accomplished by using NiII complex as the precatalyst and DMAP as the additive. The method also displays wide functional group compatibility; for example, keto, methoxy, N,N-dimethylamino, cyano, ester, and pyridyl groups are well-tolerated during the reaction process.
- Gan, Yi,Wang, Gaonan,Xie, Xin,Liu, Yuanhong
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p. 14036 - 14048
(2018/11/03)
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- METALLOENZYME INHIBITOR COMPOUNDS
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Provided are compounds having HDAC6 modulating activity, and methods of treating diseases, disorders or symptoms thereof mediated by HDAC6.
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Page/Page column 144-145
(2018/09/28)
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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 0060-0061
(2018/06/14)
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- Palladium-catalysed electrophilic aromatic C-H fluorination
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Aryl fluorides are widely used in the pharmaceutical and agrochemical industries, and recent advances have enabled their synthesis through the conversion of various functional groups. However, there is a lack of general methods for direct aromatic carbon-hydrogen (C-H) fluorination. Conventional methods require the use of either strong fluorinating reagents, which are often unselective and difficult to handle, such as elemental fluorine, or less reactive reagents that attack only the most activated arenes, which reduces the substrate scope. A method for the direct fluorination of aromatic C-H bonds could facilitate access to fluorinated derivatives of functional molecules that would otherwise be difficult to produce. For example, drug candidates with improved properties, such as increased metabolic stability or better blood-brain-barrier penetration, may become available. Here we describe an approach to catalysis and the resulting development of an undirected, palladium-catalysed method for aromatic C-H fluorination using mild electrophilic fluorinating reagents. The reaction involves a mode of catalysis that is unusual in aromatic C-H functionalization because no organometallic intermediate is formed; instead, a reactive transition-metal-fluoride electrophile is generated catalytically for the fluorination of arenes that do not otherwise react with mild fluorinating reagents. The scope and functional-group tolerance of this reaction could provide access to functional fluorinated molecules in pharmaceutical and agrochemical development that would otherwise not be readily accessible.
- Yamamoto, Kumiko,Li, Jiakun,Garber, Jeffrey A. O.,Rolfes, Julian D.,Boursalian, Gregory B.,Borghs, Jannik C.,Genicot, Christophe,Jacq, Jér?me,Van Gastel, Maurice,Neese, Frank,Ritter, Tobias
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p. 511 - 514
(2018/03/02)
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- Photocatalyst-free, Visible Light Driven, Gold Promoted Suzuki Synthesis of (Hetero)biaryls
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A visible-light driven Suzuki cross-coupling reaction was performed with colored and bench-stable arylazosulfones in the presence of Ph3PAuCl (5 mol %) as the catalyst. The absence of a photocatalyst, along with the use of commercially available and easy-to-handle arylboronic acids underline the novelty and synthetic usefulness of the protocol. A reaction mechanism involving the generation of an aryl radical as the key intermediate has been proposed on the basis of experimental investigations.
- Sauer, Christopher,Liu, Yang,De Nisi, Assunta,Protti, Stefano,Fagnoni, Maurizio,Bandini, Marco
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p. 4456 - 4459
(2017/11/20)
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- DIRECT PALLADIUM-CATALYZED AROMATIC FLUORINATION
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Provided herein are palladium complexes comprising a ligand of Formula (Α') and a ligand of Formula (B), wherein R1-R18 are as defined herein. The palladium complexes are useful in methods of fluorinating aryl and heteroaryl substrates. Further provided are compositions and kits comprising the palladium complexes.
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Paragraph 00193
(2017/09/27)
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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 0035
(2017/08/30)
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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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- A highly efficient and reusable palladium(II)/cationic 2,2′-bipyridyl-catalyzed stille coupling in water
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A water-soluble PdCl2 (NH3 )2 /cationic 2,2′ -bipyridyl system was found to be a highly efficient catalyst for Stille coupling of aryl iodides and bromides with organostannanes. The coupling reaction was conducted at 110°C in water, under aerobic conditions, in the presence of NaHCO3 as a base to afford corresponding Stille coupling products in good to high yields. When aryltributylstannanes were employed, the reactions proceeded smoothly under a very low catalyst loading (as little as 0.0001 mol %). After simple extraction, the residual aqueous phase could be reused in subsequent runs, making this Stille coupling economical. In the case of tetramethylstannane, however, a greater catalyst loading (1 mol %) and the use of tetraethylammonium iodide as a phase-transfer agent were required in order to obtain satisfactory yields.
- Wu, Wei-Yi,Liu, Ling-Jun,Chang, Fen-Ping,Cheng, Yu-Lun,Tsai, Fu-Yu
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- A deacetylation-diazotation-coupling sequence: Palladium-catalyzed C-C bond formation with acetanilides as formal leaving groups
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Acetanilides can be deacetylated and diazotized in situ, and subsequently used in Pd-catalyzed coupling reactions without isolation of the diazonium intermediate. Heck reactions, Suzuki crosscoupling reactions, and a Pd-catalyzed [2+2+1] cycloaddition hav
- Schmidt, Bernd,Berger, Rene
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supporting information
p. 463 - 476
(2013/05/08)
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- An aerobic and very fast Pd/C-catalyzed ligand-free and aqueous Suzuki reaction under mild conditions
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An aerobic, ligand-free Suzuki reaction catalyzed by Pd/C in aqueous media has been developed. This method is a very simple, efficient and mild protocol for the cross-coupling of aryl bromides with arylboronic acids, and the reactions proceeded smoothly in excellent yields within short reaction times. Control experiments demonstrated that the Pd/C-catalyzed Suzuki reaction was much quicker when performed in air or oxygen than in nitrogen. Furthermore, this protocol could be used for the synthesis of fluorinated liquid-crystalline compounds. The Pd/C catalyst could be recovered and recycled efficiently at least ten times without significant loss of catalytic activity. Copyright
- Liu, Chun,Rao, Xiaofeng,Zhang, Yixia,Li, Xinmin,Qiu, Jieshan,Jin, Zilin
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supporting information
p. 4345 - 4350
(2013/07/26)
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- ORGANOZINC COMPLEXES AND PROCESSES FOR MAKING AND USING THE SAME
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Processes for making an organozinc reagents are disclosed comprising reacting (A) organomagnesium or organozinc complexes with (B) at least one coordination compound comprising one or more carboxylate groups and/or alcoholate groups and/or tertiary amine groups, optionally in combination with zinc ions and/or lithium ions and/or halide ions, wherein the halide ions are selected from chloride, bromide and iodide, the organozinc complex comprises an aryl group, a heteroaryl group or a benzyl group when the coordinating compound is a chelating polyamine, and the reaction is conducted in the presence of zinc complexed with at least one coordinating compound when reactant (A) comprises at least one organomagnesium complex. The resulting organozinc reagents may optionally be isolated from solvents to obtain a solid reagent. The reagents may be used for making organic compounds via Negishi cross-coupling reactions or via aldehyde and/or ketone oxidative addition reactions. The organozinc reagents are stable and, due to their high selectivity, permit maintenance of sensitive functional groups such as aldehydes during cross-coupling.
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Page/Page column 28; 31
(2012/07/13)
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- Palladium nanoparticles supported on silicadiphenyl phosphinite (SDPP) as efficient catalyst for Mizoroki-Heck and Suzuki-Miyaura coupling reactions
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A very easy method is described for direct phosphorylation of silica gel to afford silica diphenylphosphinite (SDPP). This new phosphorylated silica contains higher amounts of P(III) moiety compared to the method based on the sol-gel technique. The phosphorylated silica reacts with Pd(II) to produce nano Pd(0)/SDPP which was characterized by different techniques. The obtained nano Pd(0) catalyst exhibited excellent reactivity and stability in the Mizoroki-Heck and Suzuki-Miyaura cross-coupling reactions with different aryl iodides and bromides. This heterogeneous catalyst can be easily recovered and reused in several runs.
- Iranpoor, Nasser,Firouzabadi, Habib,Motevalli, Somayeh,Talebi, Mohsen
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supporting information; experimental part
p. 118 - 124
(2012/05/20)
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- Preparation of solid salt-stabilized functionalized organozinc compounds and their application to cross-coupling and carbonyl addition reactions
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Powdered organozinc reagents: Various aryl and heteroaryl bromides as well as benzylic chlorides react with Mg and Zn(OPiv)2·2 LiCl (OPiv=pivalate) to provide solid organozinc reagents after solvent evaporation. These powders can be stored at room temperature under argon for months and can be manipulated in air for a short time. They undergo smooth Negishi cross-coupling and carbonyl addition reactions (see scheme). Copyright
- Bernhardt, Sebastian,Manolikakes, Georg,Kunz, Thomas,Knochel, Paul
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supporting information; experimental part
p. 9205 - 9209
(2011/10/30)
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- Green synthesis of fluorinated biaryl derivatives via thermoregulated ligand/palladium-catalyzed Suzuki reaction
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Fluorinated compounds have attracted considerable attention in pharmaceuticals, agrochemicals and material science due to their unique physical properties. This paper reports an efficient and environmentally benign protocol for the Suzuki reaction of aryl halides with fluorinated arylboronic acids over a thermoregulated ligand/palladium catalyst using water as sole medium, affording a variety of fluorinated biaryls, including fluorinated liquid crystals, in excellent yields. The catalyst could be recycled four times with high activity. The active catalyst was proved to be a palladium/ligand complex via a mercury-poisoning test.
- Liu, Ning,Liu, Chun,Jin, Zilin
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supporting information; experimental part
p. 2641 - 2647
(2011/07/09)
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- Pd-catalyzed coupling of aryl iodides with triarylbismuths as atom-economic multi-coupling organometallic nucleophiles under mild conditions
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The facile cross-coupling reactivity of triarylbismuth compounds with aryl iodides was achieved under mild heating conditions. The established catalytic protocol using Pd(OAc)2(Cy2NH)2 system exhibited high coupling reactivity with a variety of triarylbismuth and aryl iodide compounds under mild conditions. These coupling reactions were completed in short reaction time affording good to high yields of functionalized biaryl products. The studies of multi-coupling reactions with tris(4-iodophenyl)amine, 8 also furnished moderate to good yields of coupled products, 8a-8f.
- Rao, Maddali L.N.,Banerjee, Debasis,Dhanorkar, Ritesh J.
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supporting information; experimental part
p. 6101 - 6104
(2011/01/04)
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- Cross-coupling of triallyl(aryl)silanes with aryl bromides and chlorides: An alternative convenient biaryl synthesis
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Cross-coupling of a diverse range of aryl bromides with triallyl(aryl)silanes is effective in the presence of PdCl2/PCy 3 and tetrabutylammonium fluoride (TBAF) in DMSO-H2O to give various biaryls in good yields. It is worthwhile to note that the all-carbon-substituted arylsilanes, stable towards moisture, acid, and base and easily accessible, serve as a highly practical alternative to their aryl(halo)silane counterparts. A catalyst system consisting of [η3-C3H5)PdCl]2 and 2-[2,4,6-(i-Pr)3C6Ha]-C6H4PCy 2 and use of TBAF· 3 H2O in THF-H2O are effective especially for the cross-coupling with aryl chlorides. Both of the catalyst systems tolerate a broad spectrum of common functional groups. The high efficiency of reactions is presumably due to the ready cleavage of the allyl groups upon treatment with TBAF·3 H2O and an appropriate amount of water. Diallyl(diphenyl)silane also cross-couples with various aryl bromides and chlorides in good yields, whereas allyl(triphenyl)silane gives the cross-coupled products in only moderate yields. Through sequential cross-coupling of bromochlorobenzenes with different arylsilanes, a range of unsymmetrical terphenyls are accessible in good overall yields.
- Sahoo, Akhila K.,Oda, Takuro,Nakao, Yoshiaki,Hiyama, Tamejiro
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p. 1715 - 1727
(2007/10/03)
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- Palladium-catalyzed Suzuki-Miyaura cross-coupling reactions of potassium aryl- and heteroaryltrifluoroborates
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An extended study of the reactivity of potassium aryl- and heteroaryltrifluoroborates in Suzuki-Miyaura cross-coupling reactions is presented. The coupling of aryl- and electron-rich heteroaryltrifluoroborates with aryl and activated heteroaryl bromides proceeds readily under ligandless conditions. When deactivated aryl- and heteroaryltrifluoroborates are coupled with aryl and heteroaryl bromides and chlorides, a low loading (0.5-2%) of PdCl2(dppf)·CH2Cl2 efficiently catalyzes the reactions. Under either condition, reactions can generally be carried out in an open atmosphere.
- Molander, Gary A.,Biolatto, Betina
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p. 4302 - 4314
(2007/10/03)
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- Efficient Ligandless Palladium-Catalyzed Suzuki Reactions of Potassium Aryltrifluoroborates
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R1BF3K + R2X Pd(OAc) 2 (0.5% mol)→ R1-R2 K2CO 3 (3 equiv) methanol, reflux R1 = aryl or heteroaryl R2 = aryl or heteroaryl X = halide, triflate The ligandless palladium-catalyzed Suzuki cross-coupling reaction of potassium aryl- and heteroaryltrifluoroborates with aryl- or heteroaryl halides or triflates proceeds readily with very good yields. The cross coupling can be effected in methanol or water, in the open air, using Pd(OAc)2 as a catalyst in the presence of K2CO3. A variety of functional groups are tolerated.
- Molander, Gary A.,Biolatto, Betina
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p. 1867 - 1870
(2007/10/03)
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- Phase-Transfer-Catalyzed Gomberg-Bachmann Synthesis of Unsymmetrical Biarenes: A Survey of Catalysts and Substrates
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Two problems have hindered the Gomberg-Bachmann (GB) and Pschorr reactions of arenediazonium cations: the instability of the arenediazonium salts and side reactions.Arenediazonium tetrafluoroborate and hexafluorophosphate salts can be prepared in high yield and purity and can be stored safely.Unfortunately, these salts are insoluble in most nonpolar organic solvents.Crown ether complexation or other phase-transfer (pt) catalytic methodology can ameliorate this situation, and reactions conducted by the approaches outlined herein often afforded coupling or cyclization products in high yield and corresponding purity.The use of crown ethers, quarternary 'onium salts, lipophilic carboxylic acid salts, and even the polar cosolvent acetonitrile increase the utility of the ptGB reaction dramatically.Sixty examples of couplings are reported along with an assessment of selectivities.A number of examples are also presented of phase-transfer-type Pschorr cyclizations.In the latter case, the use of potassium superoxide, KO2, is introduced to suppress indazole formation.
- Beadle, James R.,Korzeniowsky, Stephen H.,Rosenberg, David E.,Garcia-Slanga, Blanche J.,Gokel, George W.
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p. 1594 - 1603
(2007/10/02)
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