- Iminophosphine-palladium(0) complexes as highly active catalysts in the Suzuki reaction. Synthesis of undecaaryl substituted corroles
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The iminophosphine-palladium(0) complex [Pd(dmfu)(P-N)] [dmfu=dimethyl fumarate; P-N=2-(PPh2)C6H4-1-CH=NC 6H4-4-OMe] is a very efficient catalyst for the Suzuki coupling. In the reaction of aryl bromides with phenylboronic acid, turnover numbers up to ca. 200,000 are obtained at 110°C in 2h. Good rates are obtained also with the sterically hindered and electronically deactivated 2-bromo-1,3,5-trimethylbenzene. The complex is able to catalyze the exhaustive arylation of 2,3,7,8,12,13,17,18-octabromo-5,10,15-triphenylcorroleCu(III) to yield the corresponding undecaaryl substituted derivative.
- Scrivanti, Alberto,Beghetto, Valentina,Matteoli, Ugo,Antonaroli, Simonetta,Marini, Alessia,Mandoj, Federica,Paolesse, Roberto,Crociani, Bruno
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- Suzuki Reaction of Aryl Bromides Using a Phosphine-Free Magnetic Nanoparticle-Supported Palladium Catalyst
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A palladium catalyst immobilized on superparaganetic nanoparticles was prepared with a palladium loading of 0.30 mmol/g. The catalyst was characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, vibrating sample magnetometry, thermogravimetric analysis, Fourier transform infrared, atomic absorption spectrophotometry, and nitrogen adsorption. The immobilized palladium catalyst was an efficient catalyst without added phosphine ligands for the Suzuki cross-coupling reaction of several aryl bromides with phenylboronic acid. The recovery of catalyst was simply by magnetic decantation in the presence of a magnet. The immobilized palladium catalyst can be reused many times without significant degradation in catalytic activity. No leaching of active palladium species into the reaction solution was detected.
- Bui, Nghia T.,Dang, Trung B.,Le, Ha V.,Phan, Nam T.S.
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Read Online
- Synthesis and biological evaluation of 3,5-substituted pyrazoles as possible antibacterial agents
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The emergence of multi-drug resistant bacteria has increased the need for novel antibiotics to help overcome what may be considered the greatest threat to modern medicine. Here we report the synthesis of fifteen novel 3,5-diaryl-1H- pyrazoles obtained via
- Asmara, Anjar P.,Bottomley, Amy L.,Harry, Elizabeth J.,Och, Anthony,Payne, Matthew,Ung, Alison T.
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- Pd-Catalysed Suzuki-Miyaura cross-coupling of aryl chlorides at low catalyst loadings in water for the synthesis of industrially important fungicides
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The Suzuki-Miyaura coupling reaction of electron-poor aryl chlorides in the synthesis of crop protection-relevant active ingredients in water is disclosed. Optimisation of the reaction conditions allowed running the reaction with 50 ppm of Pd-catalyst loading without an additional organic solvent in the cross-coupling reaction step in short reaction times. The system was optimised for the initial cross-coupling step of the large scale produced fungicides Boscalid, Fluxapyroxad and Bixafen up to 97% yield. It is also shown that the Suzuki-Miyaura reaction can be easily scaled up to 50 g using a simple product separation and purification using environmentally benign solvents in the work-up. To show the usability of this method, it was additionally applied in the three-step synthesis of the desired active ingredients.
- Goetz, Roland,Hashmi, A. Stephen K.,Orecchia, Patrizio,Petkova, Desislava Slavcheva,Rominger, Frank,Schaub, Thomas
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supporting information
p. 8169 - 8180
(2021/11/01)
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- A one-pot protocol for the fluorosulfonation and Suzuki coupling of phenols and bromophenols, streamlined access to biaryls and terphenyls
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A one-pot protocol for the fluorosulfation and Suzuki coupling of phenols is described. The tandem reaction proceeds efficiently at room temperature, and various biaryls and biaryl fluorosulfates were obtained in good to excellent yields. Furthermore, biaryl fluorosulfates were utilized as versatile building blocks for the preparation of terphenyls. The Royal Society of Chemistry 2020.
- Hu, Rui,Li, Xinmin,Ren, Changyue,Yuan, Zeli,Zhang, Hang,Zhang, Tingting
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supporting information
p. 4748 - 4753
(2020/08/17)
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- Highly efficient palladium-catalyzed cross-coupling of diarylborinic acids with arenediazoniums for practical diaryl synthesis
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A highly efficient cross-coupling of cost-effective diarylborinic acids with both isolatable and latent arenediazoniums, i.e. tetrafluoroborates and aryltriazenes, respectively, has been developed with a practical palladium catalyst system under base-free conditions in open flask at room temperature. A variety of electronically and sterically various biaryls, in particular, those bearing a coordinative ortho-substituent, could be obtained in good to excellent yields by using 0.3 mol% palladium acetate as catalyst. Features of the protocol including cost-effectiveness of diarylborinic acids, efficacy to heteroatom ortho-substituted substrates and high chemoselectivity to aryl chlorides have been clearly demonstrated in practical synthesis of fungicide Boscalid.
- Wang, Fengze,Wang, Chen,Sun, Guoping,Zou, Gang
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- Desulfurization of Diaryl(heteroaryl) Sulfoxides with Benzyne
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Two benzyne-enabled desulfurization reactions have been demonstrated which convert diaryl sulfoxides and heteroaryl sulfoxides to biaryls and desulfurized heteroarenes, respectively. The reaction accessing biaryls tolerates a variety of functional groups, such as halides, pseudohalides, and carbonyls. Mechanistic studies reveal that both reactions proceed via a common assembly process but divergent disassemblies of the generated tetraaryl(heteroaryl) sulfuranes.
- Chen, De-Li,Sun, Yan,Chen, Mengyuan,Li, Xiaojin,Zhang, Lei,Huang, Xin,Bai, Yihui,Luo, Fang,Peng, Bo
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supporting information
(2019/06/13)
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- Efficient construction of C–C bonds from aryl halides/aryl esters with arylboronic acids catalysed by palladium(II) thiourea complexes
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A new set of palladium(II) complexes comprising phenyl(thiazolyl)thiourea ligands have been successfully synthesized and characterized with the aid of analytical as well as spectral (IR, UV–visible and NMR) methods. A distorted square-planar geometry with N^S coordination mode of thiourea ligands in the new palladium complexes was corroborated by single-crystal X-ray diffraction methods. Interestingly, the palladium(II) thiourea complexes showed the highest catalytic activity with 0.1 mol% catalyst loading in Suzuki–Miyaura cross-coupling reactions utilizing a range of aryl bromides/unactivated aryl chlorides with arylboronic acids as coupling partners in aqueous–organic media. Syntheses of diaryl ketones using aryl esters and arylboronic acids as coupling partners were also achieved with low catalyst loading within 20 h. The potential of our catalyst was demonstrated by its wide substrate scope, low catalyst loadings and high isolated yield. Moreover, the influences of key parameters like solvent, base, temperature and catalyst loading were also investigated.
- Thimma Sambamoorthy, Manikandan,Rengan, Ramesh,Jan Grzegorz, Malecki
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- Green chemical synthesis of Pd nanoparticles for use as efficient catalyst in Suzuki-Miyaura cross-coupling reaction
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Herein, we report the synthesis of tiny spherical Pd nanoparticles (NPs) by green chemical method under ambient conditions using flower extract of Lantana camara plant. The size of the Pd NPs is tunable from 4.7 to 6.3?nm by systematically controlling the concentration of either metal ions or plant extract. The synthesized Pd NPs were well characterized by different spectroscopic, microscopic and diffractometric techniques. The Pd NPs offered good size-dependent catalytic activity in the Suzuki-Miyaura C-C coupling reaction under mild reaction conditions in (1: 1) water-ethanol mixture. The catalyst is stable and exhibited excellent reusability up to three cycles of coupling reaction after which the catalytic activity decreases.
- Phukan, Shreemoyee,Mahanta, Abhijit,Kakati, Dwipen,Rashid, Md. Harunar
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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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- 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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- Base-Controlled Heck, Suzuki, and Sonogashira Reactions Catalyzed by Ligand-Free Platinum or Palladium Single Atom and Sub-Nanometer Clusters
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The assumption that oxidative addition is the key step during the cross-coupling reaction of aryl halides has led to the development of a plethora of increasingly complex metal catalysts, thereby obviating in many cases the exact influence of the base, which is a simple, inexpensive, and necessary reagent for this paramount transformation. Here, a combined experimental and computational study shows that the oxidative addition is not the single kinetically relevant step in different cross-coupling reactions catalyzed by sub-nanometer Pt or Pd species, since the reactivity control is shifted toward subtle changes in the base. The exposed metal atoms in the cluster cooperate to enable an extremely easy oxidative addition of the aryl halide, even chlorides, and allow the base to bifurcate the coupling. With sub-nanometer Pd species, amines drive to the Heck reaction, carbonate drives to the Sonogahira reaction, and phosphate drives to the Suzuki reaction, while for Pt clusters and single atoms, good conversion is only achieved using acetate as a base. This base-controlled orthogonal reactivity with ligand-free catalysts opens new avenues in the design of cross-coupling reactions in organic synthesis.
- Fernández, Estefanía,Rivero-Crespo, Miguel A.,Domínguez, Irene,Rubio-Marqués, Paula,Oliver-Meseguer, Judit,Liu, Lichen,Cabrero-Antonino, María,Gavara, Rafael,Hernández-Garrido, Juan C.,Boronat, Mercedes,Leyva-Pérez, Antonio,Corma, Avelino
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supporting information
p. 1928 - 1940
(2019/02/14)
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- Visible light mediated desilylative C(sp2)-C(sp2) cross-coupling reactions of arylsilanes with aryldiazonium salts under Au(i)/Au(iii) catalysis
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Desilylative C(sp2)-C(sp2) cross-coupling reactions of arylsilanes with aryldiazonium salts under Au(i)/photoredox catalysis have been reported. The addition of Cu-salts as catalysts was found to be crucial for the success of this tr
- Chakrabarty, Indradweep,Akram, Manjur O.,Biswas, Suprakash,Patil, Nitin T.
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supporting information
p. 7223 - 7226
(2018/07/03)
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- Highly active and reusable hydrotalcite-supported Pd(0) catalyst for Suzuki coupling reactions of aryl bromides and chlorides
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A palladium(0) nanocluster supported on hydrotalcite has been prepared and tested for the Suzuki coupling reaction. The prepared catalyst showed very efficient catalytic activity for cross coupling of iodo- and bromoarenes under very mild reaction conditions, affording >90% yield. Under the optimized reaction conditions, chloroarenenes also showed very good reactivity. Transmission electron microscopic imaging data showed the formation of very small Pd(0)-nanoclusters (d = 2.2 ± 0.5 nm) well dispersed on the support, which enhanced the activity and stability of the catalyst for the Suzuki cross-coupling reaction. This catalytic system offers an easy method of preparation with good activity and reusability up to five cycles.
- Karanjit, Sangita,Kashihara, Masaya,Nakayama, Atsushi,Shrestha, Lok Kumar,Ariga, Katsuhiko,Namba, Kosuke
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supporting information
p. 948 - 954
(2018/01/27)
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- Reusable magnetic Pd:XCoy nanoalloys confined in mesoporous carbons for green Suzuki-Miyaura reactions
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We report herein PdxCoy nanoalloys confined in mesoporous carbons (Pdx-Coy@MC) prepared by an eco-friendly one-pot approach consisting in the co-assembly of readily available and non-toxic carbon precursors (phloroglucinol, glyoxal) with a porogen template (pluronic F-127) and metallic salts (H2PdCl4 and Co(NO3)2·6H2O) followed by thermal annealing. Three PdxCoy@MC materials with different alloy compositions were prepared (C1: x/y = 90/10; C2: x/y = 75/25; C3 and C4: x/y = 50/50). The nanoalloys were uniformly distributed in the carbon framework and the particle sizes depended on the alloy composition. These composites were then used for Suzuki-Miyaura reactions using either H2O or a 1:1 H2O/EtOH mixture as solvent. The Pd50Co50@MC catalyst C3 proved to be the most efficient catalyst (in terms of efficiency and magnetic recovery) affording the coupling products in good to excellent yields. After reaction, C3 was recovered quantitatively by simple magnetic separation and reused up to six times without loss of efficiency. The amount of palladium lost in the reaction mixture after magnetic separation was very low (ca. 0.1 % wt of the amount initially used).
- Enneiymy, Mohamed,Le Drian, Claude,Matei Ghimbeu, Camélia,Becht, Jean-Michel
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p. 17176 - 17182
(2018/05/29)
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- Facile Synthesis of Magnetic Hierarchical Core–Shell Structured Fe3O4@PDA-Pd@MOF Nanocomposites: Highly Integrated Multifunctional Catalysts
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A magnetic hierarchical core–shell structured Fe3O4@PDA-Pd@[Cu3(btc)2] nanocomposite has been fabricated via a facile layer-by-layer assembly method. It contains a core of polydopamine (PDA)-modified magnetic Fe3O4 nanoparticles (NPs), a transition layer of Pd NPs, and a porous outer shell of copper-based metal–organic framework (MOF) with controllable thickness. This novel nanocomposite was characterized by TEM, FTIR, XRD, XPS, N2 adsorption–desorption isotherms, and VSM. The prepared Fe3O4@PDA-Pd@[Cu3(btc)2] (n=5) nanocomposite shows ultrahigh catalytic activity for the 4-nitrophenol reduction and Suzuki–Miyaura coupling reactions of aryl halides (Br, Cl) with arylboronic acids. Moreover, the nanocomposite also can be easily separated by an external magnet and reused at least 8 runs with excellent yields for both the reactions. The catalyst has outstanding catalytic performance, mainly because the integration of [Cu3(btc)2] with Fe3O4@PDA-Pd that combines the advantages of each component could exhibit a synergistic effect in the catalytic system.
- Ma, Rong,Yang, Pengbo,Ma, Yao,Bian, Fengling
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p. 1446 - 1454
(2018/03/30)
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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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- A phosphine-free, atom-efficient cross-coupling of aryl iodides with triarylindiums or trialkynylindiums catalyzed by immobilization of palladium(0) in MCM-41
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The first phosphine-free heterogeneous atom-efficient cross-coupling reaction of aryl iodides with triarylindiums or trialkynylindiums was achieved in THF at 68 °C by using 1 mol% of MCM-41-immobilized palladium(0)-Schiff base complex [MCM-41-N,N-Pd(0)] as catalyst, yielding a variety of unsymmetrical biaryls and arylalkynes in good to excellent yields. The heterogeneous palladium(0) catalyst could easily be prepared via a simple procedure from commercially readily available reagents, and recovered by filtration of the reaction solution and recycled at least 10 times without significant loss of activity.
- Lei, Zhiwei,Liu, Haiyi,Cai, Mingzhong
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- Pd nanoparticles on reverse phase silica gel as recyclable catalyst for Suzuki-Miyaura cross coupling reaction and hydrogenation in water
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Two catalytic systems, consisting of palladium nanoparticles supported by reverse phase amino functionalized silica are utilized as catalysts for Suzuki-Miyaura reaction and hydrogenation in water. The catalysts were developed by modifying silica into bidentate ligands, using either 2-pyridinecarboxaldehyde or 2,2′-bipyridine-4,4′-dicarboxylic acid. The synthesized catalysts showed quantitative reaction yields and recyclability with negligible leaching of Pd nanoparticles. Various characterization techniques including XPS, ICP-MS, SEM, BET, XRD, TEM, 1H- and 13C- NMR are used to verify the efficiency of the catalysts.
- Shabbir, Saira,Lee, Sinyoung,Lim, Minkyung,Lee, Heejin,Ko, Hyeji,Lee, Youngbok,Rhee, Hakjune
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p. 296 - 304
(2017/07/12)
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- MCM-41-immobilised nitrogen and sulfur mixed tridentate palladium(0) complex: A highly efficient and recyclable catalyst for the Suzuki reaction of aryl bromides in air
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The novel MCM-41-immobilised nitrogen and sulfur mixed tridentate palladium(0) complex [MCM-41-2N,S-Pd(0)] was prepared from 3-(2-aminoethylamino) propyltrimethoxysilane by immobilisation on MCM-41, followed by reaction with thiophene-2-carboxaldehyde and PdCl2 and then reduction with hydrazine hydrate. This phosphine-free heterogeneous palladium(0) complex was a highly active catalyst for the Suzuki reaction of aryl bromides in air and could be recycled at least 8 times without significant loss of activity.
- Liu, Dayi,Wang, Pingping,Ai, Jingting,Cai, Mingzhong
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p. 186 - 191
(2017/03/24)
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- Synthesis of zwitterionic palladium complexes and their application as catalysts in cross-coupling reactions of aryl, heteroaryl and benzyl bromides with organoboron reagents in neat water
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N-(3-Chloro-2-quinoxalinyl)-N′-arylimidazolium salts (aryl = 2,6-diisopropylphenyl [HL1Cl]Cl, aryl = mesityl [HL2Cl]Cl) have been synthesized by treating 2,3-dichloroquinoxaline with the corresponding N′-arylimidazole in neat water. Facile reactions of these imidazolium salts with Pd(PPh3)4 and Pd2(dba)3/PPh3 (dba = dibenzyledene acetone) at 50 °C have afforded zwitterionic palladium(ii) complexes [Pd(HL1)(PPh3)Cl2] (I) and [Pd(HL2)(PPh3)Cl2] (II) in excellent yields. I and II have been tested for their ability to catalyze Suzuki-Miyaura cross coupling (SMC) reactions in neat water/K2CO3 and are found to be highly active for carrying out these reactions between aryl bromides and organoboron reagents. Furthermore, the scope of the catalyst I was also examined by employing (hetero)aryl bromides, hydrophilic aryl bromides, benzyl bromides and various organoboron reagents. More than 80 aryl/benzyl bromide-arylboronic acid combinations were screened in neat water/K2CO3 and it was found that I was a versatile catalyst, which produced biaryls/diarylmethanes in excellent yields. A TON of 82 000 was achieved by using I. Studies on the mechanism have also been carried out to investigate the involvement of carbene complexes in the catalytic path. Poison tests and a two-phase test were also conducted and the results are reported.
- Ramakrishna,Dastagiri Reddy
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supporting information
p. 8598 - 8610
(2017/07/12)
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- Compounds
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Pyrimidone compounds of formula (I): are inhibitors of the enzyme Lp-PLA2 and are of use in treating atherosclerosis.
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Page/Page column 14; 22
(2016/05/11)
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- Transition-Metal-Free Cross-Coupling of Aryl Halides with Arylstannanes
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Transition-metal-free LiCl-promoted cross-coupling reactions of tetraphenyltin, trichlorophenyl-, dichlorodiphenyl-, and chlorotriphenylstannanes with aryl halides in DMF provided access to biaryls in good to high yields. Up to four phenyl groups were transferred from the organostannanes substrates. The aryls bearing electron-withdrawing groups in either halides or organotin substrates gave coupling products in higher yields. The methodology has been applied for the efficient synthesis of ipriflavones.
- He, Qing,Wang, Liwen,Liang, Yong,Zhang, Zunting,Wnuk, Stanislaw F.
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p. 9422 - 9427
(2016/10/17)
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- A atom-efficient cross-coupling reaction of aryl iodides with triarylbismuths catalyzed by immobilization of palladium(II)-Schiff base complex in MCM-41
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The first phosphine-free heterogeneous atom-efficient cross-coupling of aryl iodides with triarylbismuths was achieved in NMP using K2CO3 as base at 110 °C in the presence of 2 mol % of an MCM-41-immobilized palladium(II)-Schiff base complex [MCM-41-N,N-Pd(OAc)2], yielding a variety of unsymmetrical biaryls in good to excellent yields. This new heterogeneous palladium catalyst exhibits high catalytic activity and can be recovered by a simple filtration of the reaction solution and recycled for at least 10 consecutive trials without any decreases in activity. Our system not only avoids the use of phosphine ligands, but also solves the basic problem of palladium catalyst recovery and reuse.
- Xu, Caifeng,Yin, Lin,Huang, Bin,Liu, Haiyi,Cai, Mingzhong
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p. 2065 - 2071
(2016/04/09)
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- Palladium Supported on Metformin-Functionalized Magnetic Polymer Nanocomposites: A Highly Efficient and Reusable Catalyst for the Suzuki–Miyaura Coupling Reaction
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In this paper, a novel magnetically responsive nanocatalyst, Pd/Fe3O4@PMAA-Met (PMAA=poly(methacrylic acid), Met=metformin), has been successfully prepared by immobilizing palladium on the surface of metformin-functionalized magnetic polymer nanocomposites. This novel nanocatalyst was characterized by FTIR, XRD, TEM, X-ray photoelectron spectroscopy (XPS), and vibrating sample magnetometry (VSM). The prepared nanocatalyst showed excellent catalytic activity for Suzuki–Miyaura coupling reactions of aryl halides (I, Br, Cl) with arylboronic acids even at palladium loadings of 0.01–0.0007 mol % and the turnover frequency (TOF) reached up to 125 714 h?1. The excellent activity of this Pd/Fe3O4@PMAA-Met catalyst could be attributed to a “release and catch” catalytic mechanism as well as its nanometer size. This nanocatalyst could be simply separated with an external magnet and reused at least twelve times with excellent yields achieved.
- Yang, Pengbo,Ma, Rong,Bian, Fengling
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p. 3746 - 3754
(2016/12/24)
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- Suzuki–Miyaura Cross-Coupling in Aqueous Medium Using Recyclable Palladium/Amide-Silica Catalyst
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Abstract: Silica-immobilized benzamide palladium complex was prepared and characterized. The complex exhibits excellent catalytic activity and stability for Suzuki–Miyaura cross-coupling reaction under mild aqueous reaction condition. Various aryl bromide
- Mondal, Manoj,Dewan, Anindita,Begum, Tahshina,Gogoi, Pradip K.,Thakur, Ashim Jyoti,Bora, Utpal
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p. 1718 - 1728
(2016/08/30)
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- Analysis of the water extract of waste papaya bark ash and its implications as an in situ base in the ligand-free recyclable Suzuki-Miyaura coupling reaction
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The conversion of waste papaya-bark to ash-water extract via low-temperature combustion, and its utilisation as an efficient and environmentally friendly in situ basic medium for the Suzuki-Miyaura cross-coupling reaction at room temperature are reported.
- Sarmah, Manashi,Dewan, Anindita,Mondal, Manoj,Thakur, Ashim J.,Bora, Utpal
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p. 28981 - 28985
(2016/04/09)
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- Highly efficient palladium(II) hydrazone based catalysts for the Suzuki coupling reaction in aqueous medium
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Synthesis of a new family of air stable palladium(ii)benzhydrazone complexes of the general formula [PdCl(PPh3)(L)] (where HL = thiophene aldehyde benzhydrazones) incorporating PPh3 and chloride as co-ligands has been described through a single and convenient step with good yields. All the new complexes have been fully characterized by means of elemental analysis, IR, UV-vis, and NMR spectral methods. The molecular structures of three of the complexes were determined by single crystal X-ray crystallography, which confirm the coordination mode of benzhydrazone and reveal the presence of a distorted square planar geometry around the Pd ion. The complexes 1-5 (0.05 mol%) have been found to be a highly active catalytic system in the mono and double Suzuki-Miyaura cross coupling reaction of deactivated aryl and heteroaryl bromides with different types of aryl boronic acids in neat water and the maximum yield was up to >99%. Notably, these catalysts work well with ultra-low loading of the catalysts and show high turnover numbers in a short time towards different substrates. Moreover, the catalysts could be simply recovered and reused five times without significant loss of efficiency.
- Muthumari, Subramanian,Ramesh, Rengan
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p. 52101 - 52112
(2016/06/13)
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- A self-assembled bisoxazoline/Pd composite microsphere as an excellent catalyst for Suzuki-Miyaura coupling reactions
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A palladium complex based on a novel oxazoline, a solid microsphere catalyst, was successfully prepared. The structure and composition of the solid catalyst were characterized by SEM, 1H NMR, TGA and FT-IR. This catalyst exhibits high catalytic activity for Suzuki-Miyaura cross-coupling reactions of various aryl halides and arylboronic acids in aqueous media. Moreover, the catalyst shows outstanding stability and reusability, and it can be recovered simply and effectively and reused eight times without any activity decrease.
- Wang, Junke,Zong, Yingxiao,Wang, Xicun,Hu, Yulai,Yue, Guoren,Pan, Yi
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supporting information
p. 967 - 973
(2016/02/27)
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- Synthesis, structure and catalytic applications of octahedral nickel(II) benzoylhydrazone complex: Suzuki-Miyaura cross-coupling reaction of aryl bromides with arylboronic acid
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A simple route for the synthesis of a new octahedral nickel(II) complex (1) containing 4-chloro-benzoic acid pyridin-2-ylmethylene-hydrazide ligand (HL, where H represents the dissociable proton) has been described. The characterization of the complex having the formula [Ni(μ3-O,N,N-L)2] has been established by elemental analysis, ESI-MS, spectral methods and single crystal X-ray crystallography. Further, the new complex was found to act as an active homogeneous catalyst for the Suzuki-Miyaura reaction of substituted aryl bromides (mono and dibromides) with various arylboronic acids having different electronic effects under optimized conditions of solvent, base and catalyst loading. The biphenyl and triphenyl derivatives were obtained in moderate to excellent isolated yields.
- Suganthy, Pandimuni Kalpaga,Prabhu, Rupesh Narayana,Sridevi, Venugopal Shanmugham
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p. 127 - 132
(2016/06/01)
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- An imidazolium ionic compound-supported palladium complex as an efficient catalyst for Suzuki-Miyaura reactions in aqueous media
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A water soluble and efficient ionic compound-supported palladium complex was prepared. The structure and composition of the complex was characterized by FT-IR, NMR, ICP-OES and mass spectrometry. The complex exhibits high catalytic activity for Suzuki-Miyaura reactions in aqueous media. Moreover, the catalyst shows outstanding stability and reusability, and it can be recovered simply and effectively and reused six times without much activity decrease.
- Zong, Yingxiao,Wang, Junke,He, Yubi,Yue, Guoren,Wang, Xicun,Pan, Yi
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p. 89621 - 89626
(2016/10/03)
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- Very efficient and broad-in-scope palladium-catalyzed Hiyama cross-coupling. the role of water and copper(I) salts
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A very high-yielding Pd-catalyzed cross-coupling between aryl halides and aryl(trialkoxy)silanes is achieved in the presence of Cu(i) and a measured amount of water. This novel methodology is useful for the generation of a wide range of biaryls, particularly non-para substituted derivatives, which are usually less reported.
- Traficante, Carla I.,Mata, Ernesto G.,Delpiccolo, Carina M. L.
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p. 26796 - 26800
(2015/03/30)
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- Agglomeration of Pd0 nanoparticles causing different catalytic activities of Suzuki carbonylative cross-coupling reactions catalyzed by PdII and Pd0 immobilized on dopamine-functionalized magnetite nanoparticles
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Solvent-dispersible magnetite nanoparticles (Fe3O4) end-functionalized with amino groups were successfully prepared by a facile one-pot template-free method to immobilize PdII and Pd0 using a metal adsorption and reduction procedure. They were characterized by TEM, XRD, XPS, FT-IR and VSM. Interestingly, the PdII catalyst exhibited better catalytic activity for carbonylative cross-coupling reactions than the Pd0 catalyst. According to the catalytic activities of a variety of arylboronic acids and aryl iodides catalyzed by two kinds of Pd catalysts, the proposed reaction mechanism of Suzuki carbonylative cross-coupling reactions using the Pd catalyst was also inferred. More importantly, agglomeration of Pd0 nanoparticles was obviously observed in the TEM images of the catalysts after reactions. Therefore, agglomeration of Pd0 nanoparticles should be considered as a significant reason for different catalytic activities of the reactions catalyzed by immobilized PdII and Pd0 catalysts. Furthermore, the PdII catalyst revealed high efficiency and stability during recycling stages.
- Long, Yu,Liang, Kun,Niu, Jianrui,Tong, Xin,Yuan, Bing,Ma, Jiantai
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p. 2988 - 2996
(2015/04/14)
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- PEG Click-Triazole Palladacycle: An Efficient Precatalyst for Palladium-Catalyzed Suzuki-Miyaura and Copper-free Sonogashira Reactions in Neat Water
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A novel water-soluble, phosphine-free PEG click triazole palladacycle has been successfully synthesized. As a precatalyst, the palladacycle exhibited superior catalytic activity towards Suzuki-Miyaura and copper-free Sonogashira cross-coupling in neat water with the turnover numbers (TONs) of up to 9.8×105. In addition, the catalyst could be reused at least 3 times without significant loss of reactivity. A water-soluble PEG click triazole palladacycle has been successfully synthesized. The palladacycle exhibited superior catalytic activity towards Suzuki-Miyaura and copper-free Sonogashira cross-coupling in neat water.
- Zhang, Guofu,Zhang, Wei,Luan, Yuxin,Han, Xingwang,Ding, Chengrong
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supporting information
p. 705 - 710
(2015/12/05)
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- Palladium complexes of 2-formylpyridine thiosemicarbazone and two related ligands: Synthesis, structure and, spectral and catalytic properties
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Thiosemicarbazones of 2-formylpyridine, 2-aceylpyridine and 2-benzoylpyridine, abbreviated in general as HL-R (where H depicts the acidic hydrogen and R the fragment (R = H, Me and Ph) linked to the imine-carbon) react with [Pd(PPh3)2Cl2] in refluxing ethanol in the presence of triethylamine to afford complexes of the type [Pd(L-R)(PPh3)]Cl (1, R = H; 2, R = Me, 3, R = Ph). Structures of the complexes 1 and 3 have been determined by X-ray crystallography, and the structure of complex 2 has been optimized by DFT. In all three the thiosemicarbazone ligand binds to the metal center as a monoanionic tridentate NNS-donor forming two adjacent five-membered chelate rings, the triphenylphosphine occupies the fourth coordination site on palladium. Complexes 1-3 display intense absorptions in the visible and ultraviolet regions, which have been analyzed by TDDFT calculations. All the complexes are found to efficiently catalyze Suzuki, Heck and Sonogashira type C-C cross-coupling, and C-N coupling reactions of aryl halides with primary and secondary amines. All the catalytic reactions are found to proceed under ligand-free condition.
- Paul, Piyali,Butcher, Ray J.,Bhattacharya, Samaresh
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- Electrochemical synthesis of Pd nano particles on pencil- graphite and application for suzuki coupling reactions
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Synthesis of Pd nano particles by electrochemical deposition on pencil graphite has been carried out. Catalytic activity of these nanoparticles was tested for Suzuki coupling reactions. The heterogeneous catalyst was synthesized in 10 s and without use of hazardous reducing reagent. The catalyst showed excellent catalytic performance towards Suzuki cross coupling reaction in aqueous medium. The catalyst was characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, energy dispersive X-ray analysis, thermo gravimetric analysis, inductively coupled plasma and EDX mapping techniques. Pd nano particles were found to have monodispersed nature with average particle size of 9-10 nm in diameter. The developed catalyst can be recycled up to five cycles without significant decrease in the product yield.
- Balsane, Kishor E.,Shelkar, Radheshyam S.,Nagarkar, Jayashree M.
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p. 1817 - 1824
(2019/11/28)
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- Efficient ligand-free Hiyama cross-coupling reaction catalyzed by functionalized SBA-15-supported Pd nanoparticles
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A ligand-free Hiyama cross-coupling reaction catalyzed by functionalized SBA-15-supported Pd catalysts has been developed. The catalysts were prepared by depositing Pd nanoparticles preferentially in the micropores of the SBA-15 with hydrophobic trimethylsilyl or triphenylsilyl groups grafted on the mesopores. The nanocomposite catalysts showed excellent activities for the cross-coupling between various aryltriethoxysilanes and aryl halides under relatively mild (at 100 °C in air) reaction conditions. Moreover, the hydrophobic functionalization rendered the catalysts reusable without showing significant activity loss. The decreased activity after successive catalytic runs was attributed to a low level of Pd-leaching and a gradual collapse of mesopores of host silica. The cross-coupling protocol with the designed catalysts would be practical for use as an economical synthetic method for the construction of biphenyl derivatives. the Partner Organisations 2014.
- Huang, Shao-Hsien,Liu, Chun-Hsia,Yang, Chia-Min
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p. 2706 - 2712
(2014/05/06)
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- Nickel-catalyzed one-pot Suzuki-Miyaura cross-coupling of phenols and arylboronic acids mediated by N,N-ditosylaniline
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An efficient method for the construction of two distinct C aryl-Caryl bonds through the Ni-catalyzed Suzuki-Miyaura cross-coupling of phenols with arylboronic acids has been developed. This reaction proceeds through the in situ tosylation of phenols by using N,N-ditosylaniline as the sulfonylating reagent, which is highly active, markedly stable, and easily prepared. The scope with respect to the coupling partners - phenols and boronic acids - is broad, and sensitive functional groups are tolerated. Phenols, especially those containing an unprotected amino group, which are generally problematic for coupling under conventional one-pot conditions, are also viable substrates in this transformation.
- Chen, Liangshun,Lang, Hongyue,Fang, Lei,Zhu, Mengyun,Liu, Jinqian,Yu, Jianjun,Wang, Limin
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supporting information
p. 4953 - 4957
(2014/08/18)
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- Preparation of recoverable Fe3O4/PPy-PdII catalysts for carbonylative cross-coupling reactions
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The hierarchical porous Fe3O4/PPy-PdII catalyst has been synthesized using Fe3O4 microspheres both as chemical template and oxidant source under sonication. The catalyst characterized by TEM, XRD, FT-IR, XPS and vibrating sample magnetometry (VSM). The catalyst showed high reactivity for the carbonylative cross-coupling reaction of aryl iodides with arylboronic acids. This newly developed catalyst could be easily recovered and revealed high efficiency and high stability under the reaction conditions and during recycling stages.
- Niu, Jianrui,Xie, Miao,Zhu, Xiaohang,Long, Yu,Wang, Peng,Li, Rong,Ma, Jiantai
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p. 247 - 252
(2014/07/07)
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- Pd nanoparticles immobilized on PNIPAM-halloysite: Highly active and reusable catalyst for Suzuki-Miyaura coupling reactions in water
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Poly(N-isopropylacrylamide)-halloysite (PNIPAM-HNT) nanocomposites exhibited inverse temperature solubility with a lower critical solution temperature (LCST) in water. Palladium (Pd) nanoparticles were anchored on PNIPAM-HNT nanocomposites with various amounts of HNT from 5 to 30 wt%. These Pd catalysts exhibited excellent reactivities for Suzuki-Miyaura coupling reactions at 50-70 °C in water. In particular, Pd anchored PNIPAM/HNT (95:5 w/w ratio) nanocomposites showed excellent recyclability up to 10 times in 96% average yield by simple filtration. Copyright
- Hong, Myeng Chan,Ahn, Hyunseok,Choi, Myung Chan,Lee, Yongwoo,Kim, Jongsik,Rhee, Hakjune
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p. 156 - 161
(2014/03/21)
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- A simple and efficient tetradentate Schiff base derived palladium complex for Suzuki-Miyaura reaction in water
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A simple and efficient catalytic system based on Pd complex of tetradentate Schiff base ligands is found to be highly active (up to 99% isolated yield) for Suzuki-Miyaura reaction of aryl bromides with arylboronic acids in water at room temperature. Further the scope of this protocol has been extended to the Suzuki-Miyaura cross-coupling reaction of aryl chlorides with arylbronic acids in isopropanol.
- Dewan, Anindita,Bora, Utpal,Borah, Geetika
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p. 1689 - 1692
(2014/03/21)
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- O-Aryloxime ether analogues as novel and efficient ligands for palladium-catalyzed Suzuki-Miyaura coupling in water
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O-Aryloxime ether analogues L1-L3 were studied as ligands in palladium-catalyzed Suzuki-Miyaura cross-coupling reaction of aryl bromides and aryl boronic acids in water at room temperature. Reaction conditions for the cross-coupling were optimized using PdCl2 and Pd(OAc)2 under aerobic condition. From the three electronically diverse O-aryloxime ether ligands studied herein, the use of 1-phenyl-ethanone O-(4-chloro-phenyl)-oxime L2 exhibits the best catalytic system in the presence of K2CO 3 as the base and TBAB as the promoter.
- Mondal, Manoj,Bora, Utpal
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p. 3038 - 3040
(2014/05/20)
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- Preparation of Recoverable Pd Catalysts for Carbonylative Cross-Coupling and Hydrogenation Reactions
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We report on the synthesis, characterization and catalytic performance of new, supported PdII and Pd0 catalysts. The catalysts are characterized by TEM, XRD, FTIR, X-ray photoelectron spectroscopy, and vibrating sample magnetometry. The catalysts are found to be active in both forms, PdII and Pd0, for the carbonylative cross-coupling reaction of aryl iodides with arylboronic acids, and for the hydrogenation of aromatic nitro- and unsaturated compounds. The newly developed catalysts are prepared by a synthetic strategy that is similar to the one used for other supported catalysts but are easier to recover-they can be recycled by magnetic separation from liquid phase reactions-and can be used for at least 5 consecutive trials without any decrease in activity.
- Niu, Jian-Rui,Huo, Xing,Zhang, Feng-Wei,Wang, Hai-Bo,Zhao, Ping,Hu, Wu-Quan,Ma, Jiantai,Li, Rong
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p. 349 - 354
(2013/03/13)
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- Recyclable palladium(II) imino-pyridine complex immobilized on mesoporous silica as a highly active and recoverable catalyst for Suzuki-Miyaura coupling reactions in aqueous medium
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A new mesoporous silica supported palladium imino-pyridine complex was successfully prepared by attaching palladium acetates to a novel imino-pyridine ligand functionalized MCM-41. The as-prepared catalyst was characterized by ICP-AES, XRD, FTIR, SEM, and TEM. It was found to be an efficient catalyst for Suzuki-Miyaura coupling reactions in aqueous medium. The reactions of various aryl bromides with arylboronic acids could be carried out under aerobic and low Pd loading (0.1 mol %) conditions with good to excellent yields, and very low Pd leaching (0.2 ppm) was detected. Moreover, the supported catalyst could be simply recovered and reused several times without significant loss of efficiency.
- Zhang, Qiang,Su, Hong,Luo, Jun,Wei, Yunyang
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p. 447 - 454
(2013/02/23)
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- Nanoparticulate palladium catalyst stabilized by supported on feather keratin for Suzuki coupling reaction
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Palladium nanoparticles supported in a feather keratin matrix were efficient catalyst for the coupling reactions of aryl bromides with arylboronic acid in aqueous medium under mild reaction conditions. The biopolymer-based catalyst demonstrated excellent activity for substrates with a wide range of functional groups. The product biaryls were precipitated from the reaction mixture with good to excellent yields and purities. The catalyst was recovered from the reaction solution easily by simple filtration, and can be reused at least seven times.
- Ma, Hengchang,Bao, Zhikang,Han, Guobin,Yang, Ningning,Xu, Yufei,Yang, Zengming,Cao, Wei,Ma, Yuan
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p. 578 - 584
(2013/08/25)
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- α-Hydroxyimine palladium complexes: Synthesis, molecular structure, and their activities towards the Suzuki-Miyaura cross-coupling reaction
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An activity-promoting strategy for phosphine-free catalytic systems is presented in this study. The strategy is based on a series of non-conjugated N,O ligands with bulky substituents, [Ar-NC(R)-(R)C(CH3)OH] (L1, R = Acenaphthyl, Ar = 2,6-diiso
- Tang, Xiao,Huang, Ying-Tang,Liu, Huan,Liu, Rui-Zhi,Shen, Dong-Sheng,Liu, Ning,Liu, Feng-Shou
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- A palladium complex with functionalized β-cyclodextrin: A promising catalyst featuring recognition abilities for Suzuki-Miyaura coupling reactions in water
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A water-soluble palladium complex (PdLnβ-CD) was designed and prepared based on functionalized β-cyclodextrin. It showed high turnover numbers (TONs) and turnover frequencies (TOFs) of up to 9.9 × 108 and 4.9 × 108 h-1, respectively, in aqueous Suzuki-Miyaura coupling reactions. The detailed reason for the excellent catalytic activity was studied.
- Zhang, Guofu,Luan, Yuxin,Han, Xingwang,Wang, Yong,Wen, Xin,Ding, Chengrong,Gao, Jianrong
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supporting information
p. 2081 - 2085
(2013/09/24)
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- Palladium(II) thiosemicarbazone-catalyzed Suzuki-Miyaura cross-coupling reactions of aryl halides
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A new air-and moisture-stable palladium(II) complex bearing pyridoxal thiosemicarbazone ligand has been synthesized. The synthesized complex was characterized by analytical and spectral methods. The molecular structure of the complex was confirmed by X-ray diffraction method. The palladium(II) complex was used as potential catalyst for Suzuki-Miyaura coupling reaction of several aryl halides under optimized conditions.
- Pandiarajan, Devaraj,Ramesh, Rengan,Liu, Yu,Suresh, Rajamanickam
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- Controlled interaction of benzaldehyde thiosemicarbazones with palladium: Formation of bis-complexes with cis-geometry and organopalladium complexes, and their catalytic application in C-C and C-N coupling
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Reaction of a 1 : 1 mixture of 4-R-benzaldehyde thiosemicarbazone (R = OCH3, CH3, H, Cl and NO2) and 2-picolinic acid with an equivalent quantity of Na2[PdCl4] in ethanolic medium, under relatively mild reflux, affords a group of complexes of type [Pd(NS-R)2] as the major product and another family of complexes of type [{Pd(CNS-R)}n] as the minor product (where NS-R and CNS-R denote the N,S- and C,N,S-coordinated thiosemicarbazone, respectively). The [{Pd(CNS-R)}n] complexes are conveniently obtained in good yields from similar reactions carried out under prolonged reflux. The sulfur-bridge in the [{Pd(CNS-R)}n] complexes undergoes facile cleavage upon their reaction with triphenylphosphine to yield complexes of type [Pd(CNS-R)(PPh 3)]. Crystal structures of [Pd(NS-OCH3)2], [Pd(NS-CH3)2], [Pd(NS-Cl)2], [Pd(CNS-CH 3)(PPh3)], [Pd(CNS-H)(PPh3)] and [Pd(CNS-Cl)(PPh3)] have been determined. In the [Pd(NS-R) 2] complexes the thiosemicarbazones are coordinated to the metal center, via dissociation of the acidic proton, as monoanionic bidentate N,S-donors forming five-membered chelate rings, while in the [Pd(CNS-R)(PPh 3)] complexes they are coordinated to palladium, via dissociation of the acidic proton and activation of an ortho C-H bond, as dianionic tridentate C,N,S-donors forming two adjacent five-membered chelate rings. The [Pd(NS-R)2] and [Pd(CNS-R)(PPh3)] complexes show characteristic 1H NMR signals, and in dichloromethane solution they all display intense absorptions in the visible and ultraviolet regions. The [Pd(NS-R)2] and [Pd(CNS-R)(PPh3)] complexes have shown notable efficiency in catalyzing C-C and C-N coupling reactions. The Royal Society of Chemistry 2013.
- Dutta, Jayita,Bhattacharya, Samaresh
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p. 10707 - 10721
(2013/09/02)
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- Suzuki-Miyaura cross-coupling reactions using a low-leaching and highly recyclable gold-supported palladium material and two types of microwave equipments
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We designed Suzuki-Miyaura cross-coupling reactions in conjunction with sulfur-modified Au-supported Pd material (SAPd) and two types of microwaves, single-mode and multi-mode. The entire microwave-facilitated process provided advantages over conventional heating in that reactivity of the less reactive arylbromides was induced and the reaction time was reduced.
- Al-Amin, Mohammad,Akimoto, Masayoshi,Tameno, Tsuyoshi,Ohki, Yuuta,Takahashi, Naoyuki,Hoshiya, Naoyuki,Shuto, Satoshi,Arisawa, Mitsuhiro
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supporting information
p. 1142 - 1145
(2013/06/05)
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- Synthesis of Biaryl derivatives via a magnetic Pd-NPs-catalyzed one-pot diazotization-cross-coupling reaction
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A magnetic Pd-NPs-catalyzed one-pot diazotizationcross-coupling reaction of anilines and arylboronic acids was developed. Biaryl derivatives were therefore synthesized in good to excellent yields. Through magnetic separation, the catalyst could be recovered and reused for five times. There were several obvious advantages such as broad applicability, high selectivity, simply experimental operation as well as the convenient preparation, high efficiency and reusability of catalyst. Georg Thieme Verlag Stuttgart ? New York.
- Zong, Yan,Hu, Jiefeng,Sun, Peipei,Jiang, Xiaoqing
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supporting information
p. 2393 - 2396
(2013/07/19)
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