- Highly effective activation of aryl chlorides for Suzuki coupling in aqueous media using a ferrocene-based Pd(II)-diimine catalyst
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The Suzuki coupling of aryl chlorides with boronic acids using a ferrocene-containing Pd(II)-diimine complex as catalyst, in aqueous media, under microwave heating is reported. A small amount of the catalyst (0.1%) was found to be highly effective for coupling unactivated aryl chlorides with boronic acids to form sterically hindered ortho-substituted biaryls. The same catalyst also enabled the coupling of aryl bromides and iodides with various boronic acids in very high yields. The catalyst is air stable and the catalytic reaction can be completed in 15 min.
- Hanhan, Murat Emre,Martínez-Má?ez, Ramon,Ros-Lis, Jose Vicente
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Read Online
- Dual-Metal N-Heterocyclic Carbene Complex (M = Au and Pd)-Functionalized UiO-67 MOF for Alkyne Hydration-Suzuki Coupling Tandem Reaction
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Metal N-heterocyclic carbene complexes (NHC-M) have been recognized as an important class of organometallic catalysts. Herein, we demonstrate that different NHC-M (M = Au and Pd) species can be simultaneously introduced into a single metal organic framework (MOF) by direct assembly of NHC-M-decorated ligands and metal ions under solvothermal conditions. The obtained UiO-67-Au/Pd-NHBC MOF with different organometallic NHC-M species can be a highly reusable dual catalyst to sequentially promote alkyne hydration-Suzuki coupling reaction. The potential utility of this strategy is highlighted by the preparation of many more new multicatalysts of this type for various organic transformations in a sequential way.
- Dong, Ying,Li, Wen-Han,Dong, Yu-Bin
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p. 1818 - 1826
(2021/01/13)
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- Highly Active Fe3O4@SBA-15@NHC-Pd Catalyst for Suzuki–Miyaura Cross-Coupling Reaction
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A novel Pd-NHC functionalized magnetic Fe3O4@SBA-15@NHC-Pd was synthesized and used as an efficient heterogeneous catalyst in the Suzuki–Miyaura C–C bond formation reactions. The Fe3O4@SBA-15@NHC-Pd characterized by X-Ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Fourier Transform Infrared (FTIR) spectroscopy, Scanning Electron Microscopy (SEM), Transmission Electron Microscopy?(TEM), Energy Dispersive X-ray analysis (EDX), Thermogravimetric Analysis (TGA), Differential Thermal Analysis (DTA). The Inductively Coupled Plasma-Optical emission spectroscopy (ICP-OES)?analysis was used to determine the exact amount of Pd (0.33?wt%) in Fe3O4@SBA-15@NHC-Pd. The TEM images of the catalyst showed the existence of palladium nanoparticles immobilized in the catalyst's structure, while no reducing agent was used. The NHC moieties in the catalyst structure could be stabilize Pd(0) nanoparticles prevents agglomeration. The magnetic catalyst was effectively used in the Suzuki–Miyaura cross-coupling reaction of substituted phenylboronic acid derivatives with (hetero)aryl bromides in the presence of a K2CO3 at room temperature in aqueous media and magnetic catalyst could be simply extracted from the reaction mixture by an external magnet. Different aryl bromides were converted to coupled-products in excellent yields with spectacular TOFs values (up to 1,960,339?h?1); in the presence of 1?mg of Fe3O4@SBA-15@NHC-Pd catalyst (contains 3.1 × 10–6?mol% Pd) at room temperature in aqueous media. After reusability experiments, it is found that this catalyst was effectively used up to ten times in the reaction with almost consistent catalytic efficiency. A decrease in the activity of the 10th reused catalyst was found as 9%. Graphic Abstract: [Figure not available: see fulltext.]
- ?zdemir, ?smail,Akko?, Mitat,Alt?n, Serdar,Bu?day, Nesrin,Ya?ar, Sedat
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- 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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- 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 0047-0048
(2020/06/30)
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- A catalytic system with high efficiency and recyclability based on Suzuki and Heck reaction in aqueous admicellar medium
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A recyclable and non-phosphine solid palladium (II) catalyst was prepared and characterized by HR-MS, FT-IR, XPS, EDS, TGA, SEM, TEM and ICP. The Pd-catalyst exhibited high-performance catalytic activity in Suzuki and Heck C-C coupling reactions in an environmentally benign water medium. Further, the Pd-catalyst (Z4) can be reused for 15 times with little decrease of activity through simple and efficient recovery. In addition, the turn-over number (TON) of Pd- catalyst can reach 380 at room temperature. These results proved that the Pd-catalyst has a stable structure and can be recycled many times, making the process sustainable.
- Zhang, Hao,Zhu, Ji-Hua,Hou, Fei,Quan, Zheng-Jun,Wang, Xi-Cun
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- Nickel-catalyzed cross-coupling of: O, N -chelated diarylborinates with aryl chlorides and mesylates
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A practical nickel catalyst system consisting of readily available components, trans-NiCl(Ph)(PPh3)2/[Iprmim]I/K3PO4·3H2O in toluene, has been developed for efficient cross-coupling of 3-dimethylaminopropyl diarylborinates with aryl chlorides and mesylates. A small amount of water has been found to be crucial in achieving high efficiency in the system. The nickel catalyst system displayed remarkably higher activities to aryl chlorides and mesylates than the corresponding tosylates in cross-coupling with not only diarylborinates but also diarylborinic acids, arylboronic acids, anhydrides and trifluoroborates as indicated in control experiments. A variety of electronically various biaryls could be obtained in excellent yields by using 3-5 mol% loading of the nickel catalyst while sterically hindered biaryls were obtained in comparably lower yields.
- Ren, Chao,Zeng, Jingshu,Zou, Gang
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supporting information
p. 1589 - 1596
(2019/01/23)
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- N, C-Disubstituted Biarylpalladacycles as Precatalysts for ppm Pd-Catalyzed Cross Couplings in Water under Mild Conditions
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Various monosubstitution and disubstitution patterns on the parent biarylamine skeleton characteristic of palladacycles, as well as the counterion effect, have been studied while looking for ways to increase the effectiveness of the catalyst formed under micellar catalysis conditions in water, with the goal of reducing the amount of Pd needed for coupling reactions. Several substituted palladacycles containing readily accessible ligands were chosen for evaluation. The results indicate that (1) preactivation of Pd(II) salts as precursors for Suzuki-Miyaura (SM) couplings via treatment with a reducing agent is not required; (2) reactions could be performed with approximately half the loading of Pd, relative to that previously required based on a combination of a Pd(II) salt and ligand; and (3) the most effective palladacycle precatalyst has been identified as that containing an isopropyl group on both an aryl ring and on nitrogen, together with the ligand EvanPhos and triflate as the counterion (P13). This precatalyst is also effective in other C-C bond-forming reactions, such as Heck and Sonogashira couplings. No organic solvents were needed for these processes, while the aqueous reaction medium could be recycled several times. A one-pot, four-step sequence involving Suzuki-Miyaura, reduction, alkylation, and acylation reactions highlights the potential for this precatalyst to maximize synthetic gain while minimizing costs and waste generation.
- Thakore, Ruchita R.,Takale, Balaram S.,Gallou, Fabrice,Reilly, John,Lipshutz, Bruce H.
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p. 11647 - 11657
(2019/11/29)
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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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- Mesoporous carbon supported ultrasmall palladium particles as highly active catalyst for Suzuki-Miyaura reaction
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A fast and efficient eco-friendly two-step preparation of a palladium-containing mesoporous carbon catalyst (C1) from green and readily available carbon precursors (phloroglucinol and glyoxal), a porogen template (pluronic F-127) and PdCl2 is described. Catalyst C1 contains ultra-small Pd nanoparticles (1.2 nm) uniformly dispersed in the carbon network and shows an outstanding activity for Suzuki-Miyaura reactions in pure water: extremely low amounts of palladium (10 μequiv. in most cases) are sufficient to afford almost palladium-free products (containing 0.25 ppm of precious metal without further purification steps).
- Enneiymy, Mohamed,Le Drian, Claude,Ghimbeu, Camelia Matei,Becht, Jean-Michel
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- Visible-Light-Enhanced Suzuki–Miyaura Reactions of Aryl Chlorides in Water with Pd NPs Supported on a Conjugated Nanoporous Polycarbazole
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The visible-light-enhanced catalytic activation of aryl chlorides for Suzuki–Miyaura cross-coupling (SMC) reactions is highly challenging because of the strength of the C?Cl bond. In this work, palladium nanoparticles (Pd NPs) were grown on a conjugated nanoporous polycarbazole (CNP), named Pd/CNP. The hybrid material Pd/CNP could catalyze the SMC reactions of aryl chlorides with arylboronic acids in water under blue LED irradiation at room temperature with high efficiency. This protocol exhibited good functional group tolerance and the catalyst could be recycled without significant loss of its catalytic activity. CNP not only provided photogenerated electrons to enrich the electron density of the Pd NPs but also generated holes for the activation of the arylboronic acids.
- Guo, Bin,Li, Hong-Xi,Zha, Cheng-Hao,Young, David James,Li, Hai-Yan,Lang, Jian-Ping
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p. 1421 - 1427
(2019/02/26)
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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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- Modular Functionalization of Arenes in a Triply Selective Sequence: Rapid C(sp2) and C(sp3) Coupling of C?Br, C?OTf, and C?Cl Bonds Enabled by a Single Palladium(I) Dimer
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Full control over multiple competing coupling sites would enable straightforward access to densely functionalized compound libraries. Historically, the site selection in Pd0-catalyzed functionalizations of poly(pseudo)halogenated arenes has been unpredictable, being dependent on the employed catalyst, the reaction conditions, and the substrate itself. Building on our previous report of C?Br-selective functionalization in the presence of C?OTf and C?Cl bonds, we herein complete the sequence and demonstrate the first general arylations and alkylations of C?OTf bonds (in I dimer. This allowed the realization of the first general and triply selective sequential C?C coupling (in 2D and 3D space) of C?Br followed by C?OTf and then C?Cl bonds.
- Keaveney, Sinead T.,Kundu, Gourab,Schoenebeck, Franziska
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supporting information
p. 12573 - 12577
(2018/09/18)
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- EvanPhos: A ligand for ppm level Pd-catalyzed Suzuki-Miyaura couplings in either organic solvent or water
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A new biaryl phosphine-containing platform can be constructed in only two steps. It complexes Pd(OAc)2 forming a precursor of a very active catalyst useful for Suzuki-Miyaura cross-couplings of functionalized substrates. By a combination of pre-activation, used together with the uncommon solvent EtOAc, the resulting catalyst system is effective at loadings in the ppm (0.1-0.5 mol%) range with highly functionalized reaction partners. Similar reactions run in water containing nanomicelles are as fast or faster. The derived Pd-complexed pre-catalyst possesses extended bench stability. The resulting technology represents an attractive green synthetic advance in highly valued Suzuki-Miyaura couplings.
- Landstrom, Evan B.,Handa, Sachin,Aue, Donald H.,Gallou, Fabrice,Lipshutz, Bruce H.
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supporting information
p. 3436 - 3443
(2018/08/07)
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- Highly efficient and recyclable water-soluble fullerene-supported PdCl2 nanocatalyst in Suzuki-Miyaura cross-coupling reaction
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A water-soluble fullerene-supported PdCl2 nanocatalyst [C60-TEGS/PdCl2] was prepared by coordination of water-soluble fullerene nanoparticles with palladium chloride. In pure water, the catalytic activity of nanocatalyst [C60-TEGS/PdCl2] for Suzuki-Miyaura cross-coupling reaction was investigated under different reaction conditions. The results showed that biphenyl compounds could be synthesized in high yields at room temperature using 0.01 mol% of [C60-TEGS/PdCl2] as the catalyst and K2CO3 as the base with the reaction time of 4 h. The catalyst was recycled five times, and the yield clearly did not decrease.
- Li, Jingbo,Huo, Ping,Zheng, Junwei,Zhou, Xiuming,Liu, Wanyun
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p. 24231 - 24235
(2018/07/25)
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- PEPPSI-type complexes with small NHC ligands obtained according to the new method efficiently catalyzed Suzuki-Miyaura reaction
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A series of 13 new PEPPSI-type complexes with small NHC ligands and differently substituted imidazoles were prepared using as substrates [Pd(μ-X)X(bmim-y)]2 dimer or imidazole complexes PdCl2(imidazole)2. Improvement of th
- Sikorski,Zawartka,Trzeciak
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p. 323 - 332
(2018/02/09)
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- PRODUCTION METHOD OF COUPLING REACTION PRODUCT OF ORGANIC COMPOUND HAVING LEAVING GROUP WITH ORGANOBORON COMPOUND
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PROBLEM TO BE SOLVED: To provide a production method with which a coupling product of the Suzuki-Miyaura cross-coupling reaction can be obtained without using any special ligand, with a practically available yield, and with an amount of catalyst of order of mol ppm. SOLUTION: In a production method, a coupling product is produced by making an organic compound having a leaving group selected from bromine atom, iodine atom, methanesulfonyloxy group, and trifluoromethanesulfonyloxy group react with an organoboron compound in the presence of a catalyst, a base and a solvent, in which the catalyst is a palladium salt with an amount of 10 mol ppm or less, the base is a carbonate, and the solvent is a mixed solvent including ethanol or isopropanol and water, and the reaction is carried out in an oxygen-containing gaseous atmosphere. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT
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Paragraph 0025-0027
(2018/05/24)
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- Application of a zwitterionic palladium complex as a metal precursor of recyclable palladium nanoparticles for catalyzing Suzuki-Miyaura coupling reactions
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An efficient recyclable catalyst system for Suzuki-Miyaura coupling reactions in water was developed based on a zwitterionic palladium complex bearing an imidazolium-based carbon donor and tricyclohexylphopshine. The complex served as an effective metal p
- Lee, Jhen-Yi,Tzeng, Ru-Jiun,Wang, Mu-Cheng,Lee, Hon Man
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- Highly active palladium catalysts with bisacetylacetonate ligands for suzuki miyaura cross-coupling reactions in mild conditions
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In the presence of Pd(OAc)2, three bisacetylacetonate ligands were demonstrated to form a highly efficient catalyst for the SuzukiMiyaura cross-coupling reactions. The most active bisacetylacetonate ligand with anthracene groups on the backbone
- Liu, Wanyun,Xiong, Dayan,Huo, Ping,Mei, Guangquan
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supporting information
p. 1550 - 1552
(2017/11/04)
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- Novel phosphorus-coordinated palladium(II) complexes derived from 3,5-disubstituted-1H-1,2,4-diazaphospholes: Synthesis and catalytic application in Suzuki-Miyaura cross-coupling reactions
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Four novel phosphorus-coordinated palladium(II) complexes(I-IV) were easily prepared by the reaction of 3,5-disubstituted-1H-1,2,4-diazaphospholes with Pd(CH3CN)2Cl2at room temperature and characterized. The catalytic activity of palladium(II) complexes was further evaluated in Suzuki-Miyaura reaction of aryl halides with arylboronic acids, giving the biphenyl derivatives in good yields.
- Jia, Xuefeng,Zhao, Fang
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p. 145 - 149
(2017/03/09)
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- Highly Efficient Bulky α-Diimine Palladium Complexes for Suzuki-Miyaura Cross-Coupling Reaction
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A series of bulky 9,10-dihydro-9,10-ethanoanthracene-11,12-diimine methyl palladium chloride complexes (C1—C6) with different steric and electronic substituent have been applied in Suzuki-Miyaura cross-coupling reactions. The influence of these substituents was investigated by comparing the catalytic performance of the complexes in the cross-coupling reactions and it can be found that the complex with bulky and electron-donating substituent is facilitated for the cross-coupling reaction of aryl halides with arylboronic acids under ambient atmosphere. The most active complex shows a wide substrate scope in excellent yields using very low catalyst concentration of 0.01 mol%.
- Huo, Ping,Li, Jingbo,Liu, Wanyun,Mei, Guangquan
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p. 363 - 367
(2017/03/24)
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- Invisible Chelating Effect Exhibited between Carbodicarbene and Phosphine through π-π Interaction and Implication in the Cross-Coupling Reaction
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Palladium complexes supported with the mixed ligands carbodicarbene (CDC) and different phosphine ligands (PPh3, PTol3, and PCy3) were prepared, and their molecular structures were characterized. Examination of the structures of 2-PPh3 and 2-PTol3 with cis configuration discloses the existence of an unexpected π-π interaction between one phenyl group of the phosphine and the benzimidazole ring of a CDC. The palladium complex 2-PPh3 is an active Suzuki-Miyaura catalyst with a wide scope of substrates containing various functional groups and steric demands. In contrast to electron-withdrawing aryl bromide, the yield of product for electron-rich substrates was improved by adding a catalytic amount of DMSO under aerobic conditions. The solution NMR and structural analysis has revealed that the intramolecular π-π interaction between CDC and phosphine ligands has a positive influence on the activity of the reaction, which is further supported by quantum chemical calculations.
- Shih, Wei-Chih,Chiang, Yun-Ting,Wang, Qing,Wu, Ming-Chun,Yap, Glenn P. A.,Zhao, Lili,Ong, Tiow-Gan
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supporting information
p. 4287 - 4297
(2017/11/20)
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- Highly bulky and stable geometry-constrained iminopyridines: Synthesis, structure and application in Pd-catalyzed Suzuki coupling of aryl chlorides
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A series of bulky geometry-constrained iminopyridylpalladium chlorides were developed. The steric environment adjacent to the nitrogen atom in the pyridine rings and diimine parts enhanced the thermal stability of the palladium species. Bulkier groups at the imino group stabilized the palladium species and the corresponding palladium chlorides showed high activities in the coupling reaction of aryl chlorides.
- Lai, Yi,Zong, Zhijian,Tang, Yujie,Mo, Weimin,Sun, Nan,Hu, Baoxiang,Shen, Zhenlu,Jin, Liqun,Sun, Wen-Hua,Hu, Xinquan
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p. 213 - 221
(2017/02/15)
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- Rapid threefold cross-couplings with sterically bulky triarylbismuths under Pd-Cu dual catalysis
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The threefold cross-coupling reactivity of sterically highly demanding bulky triarylbismuths was addressed with task specific Pd-Cu dual catalytic conditions. In this study, an unprecedented hitherto unknown cross-coupling reactivity of sterically bulky triarylbismuths was demonstrated with a diverse range of aryl iodides and bromides. The intermediacy and in situ formation of arylcopper was probed with mesitylcopper in support of the proposed dual catalysis. This study opened up an easy way forward for application of sterically bulky bismuth reagents in threefold aryl-aryl coupling reactions.
- Rao, Maddali L. N.,Dhanorkar, Ritesh J.
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p. 1012 - 1017
(2016/01/16)
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- A reusable heterogeneous catalyst without leaking palladium for highly-efficient Suzuki-Miyaura reaction in pure water under air
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Herein, we report a heterogenous catalyst (Pd@FSM) by immobilization of a novel Pd2+ sensor as promoter over mesoporous silica. Pd@FSM with a high palladium loading of ca. 11 mg g-1 exhibited superior catalytic activity for Suzuki-Miyaura cross-couplings and a catalyst loading of 0.05 mol% is typically sufficient to achieve excellent reaction yields. Notably, the reaction is typically carried out in water without removing atmospheric oxygen. The catalyst is conveniently recycled and remains highly active even after being recycled 5 times. During this process, loss of palladium from the solid support of the catalyst is negligible. Furthermore, the catalyst can be stored in air for at least three months without loss of its catalytic activity. This work provides a new approach to developing heterogeneous palladium catalysts by combing materials and fluorescent sensors.
- Cai, Qi,Liang, Gaosheng,Xu, Yufang,Qian, Xuhong,Zhu, Weiping
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p. 60996 - 61000
(2016/07/12)
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- Highly efficient palladium-catalyzed suzukiMiyaura cross-coupling with 9,10-dihydro-9,10-ethanoanthracene-11,12-diimine ligands under mild aerobic conditions
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A novel 9,10-dihydro-9,10-ethanoanthracene-11,12-diimine/ Pd(OAc)2system has been demonstrated to form a highly efficient catalyst for the SuzukiMiyaura cross-coupling of various aryl bromides and activated aryl chlorides with arylboronic acids
- Huo, Ping,Li, Jingbo,Liu, Wanyun,He, Xiaohui,Mei, Guangquan
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supporting information
p. 454 - 456
(2016/05/09)
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- Efficient benzocyclohexane-ketoamine ligands for palladium-catalyzed Suzuki-Miyaura cross-coupling reaction
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In the presence of 0.02 mol% Pd(OAc)2, a series of benzocyclohexane-ketoamine ligands were demonstrated to form a highly efficient catalyst for the Suzuki-Miyaura cross-coupling of various aryl halides with arylboronic acids in ethanol/aqueous media under ambient atmosphere.
- Liu, Wanyun,Xiong, Dayan,Huo, Ping,He, Xiaohui,Mei, Guangquan
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supporting information
p. 1232 - 1234
(2016/11/09)
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- Liquid-Assisted Grinding Accelerating: Suzuki-Miyaura Reaction of Aryl Chlorides under High-Speed Ball-Milling Conditions
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The effect of liquid-assisted grinding has been studied using mechanical Suzuki-Miyaura reaction of aryl chlorides as the model reaction. Catalytic systems of Davephos and PCy3 are tested respectively showing strong influences from different liquids. Unexpected improvement of yield over 55% is observed using alcohols as additives, which is explained by in situ formed alkoxides and their participation in oxidative addition. Further expansion of substrates using Pd(OAc)2/PCy3/MeOH system gives desired products in good to high yields.
- Jiang, Zhi-Jiang,Li, Zhen-Hua,Yu, Jing-Bo,Su, Wei-Ke
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p. 10049 - 10055
(2016/11/02)
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- N-heterocyclic carbene coordinated heterogeneous Pd nanoparticles as catalysts for suzuki-miyaura coupling
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Palladium nanoparticle (Pd NP) catalysts immobilized in a polymer with an N-heterocyclic carbene (NHC) moiety (PICBNHC-Pd) have been developed, wherein the NHC moiety plays dual roles as a crosslinker and a ligand to activate the Pd NPs. The presence of both Pd NPs and NHC was confirmed by STEM/EDS and SR-MAS NMR analyses, respectively. This PICB-NHC-Pd catalyst showed excellent activity in the Suzuki-Miyaura coupling reaction without leaching of Pd. Excellent results were obtained in gram-scale synthesis, and catalyst recovery/reuse experiments were completed without loss of catalyst activity.
- Min, Hyemin,Miyamura, Hiroyuki,Kobayashi, Shu
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supporting information
p. 837 - 839
(2016/07/16)
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- Hierarchical nanospheres based on Pd nanoparticles dispersed on carbon coated magnetite cores with a mesoporous ceria shell: A highly integrated multifunctional catalyst
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The design and fabrication of core-shell nanostructures with steerable morphologies and tailored performances have aroused abundant scientific studies for organic transformations. We here report the preparation of multifunctional and highly efficient core-shell microspheres, which bear a carbon-protected magnetic Fe3O4 core, a transition layer of active Pd nanoparticles (NPs) and an outer shell of mesoporous CeO2 (mCeO2). The composition and structure of the as-prepared Fe3O4@C-Pd@mCeO2 were thoroughly characterized by X-ray photoelectron spectroscopy, transmission electron microscopy, scanning electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy and Brunauer-Emmett-Teller measurements. The well-designed microspheres have high dispersibility, convenient magnetic separability and good reusability as heterogeneous nanoreactors due to their unique structure. We illustrate the high efficiency of these nanocomposites in mediating the Suzuki-Miyaura cross-coupling reaction and the reduction reaction of 4-nitrophenol (4-NP). The enhanced catalytic activity can be attributed to the synergistic effect between the CeO2 nanoparticles and noble metal NPs. A mechanism was further proposed to explain the improved catalytic activity. This peculiar core-shell nanostructure renders the nanospheres to be an approachable and attractive catalyst system for various catalytic organic industrial processes.
- Li, Yinle,Zhang, Zhuqing,Shen, Jianfeng,Ye, Mingxin
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p. 16592 - 16601
(2015/09/28)
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- Water-soluble salen-Pd complex as an efficient catalyst for Suzuki-Miyaura reaction of sterically hindered substrates in pure water
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Water-soluble 2N2O-salen ligands and their palladium complexes were synthesized and used as efficient catalysts for the Suzuki-Miyaura reactions in pure water. Notably, the reactions of substrates with sterically demanding ortho substituents (aryl bromides and/or arylboronic acids) proceed smoothly to generate corresponding products with moderate to high yields using 0.5 mol % (salph)Pd (salph=N,N′-bis(4-SO3Na-salicylidene)-1,2-phenylenediamine) as the catalyst. Importantly, the catalytic system has the wide substrate scope and the high tolerance to various functional groups, including cyano, amino, nitro, methoxy, and acetyl. Moreover, the biaryl compounds were also obtained on a multi-gram scale by simple recrystallization with the system in the absence of any organic solvent, surfactant, or phase transfer agent and the catalyst was reused directly for the next cycle. Particularly, this protocol can be applied to synthesize aryl-substituted carbazolyl compounds.
- Liu, Ya-Shuai,Gu, Ning-Ning,Liu, Ping,Ma, Xiao-Wei,Liu, Yan,Xie, Jian-Wei,Dai, Bin
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supporting information
p. 7985 - 7989
(2015/12/31)
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- Biosourced mesoporous carbon with embedded palladium nanoparticles by a one pot soft-template synthesis: Application to Suzuki reactions
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A simple, direct and environmentally-friendly one-pot preparation of a palladium-containing mesoporous carbon (Pd@MC) from a cheap, non-hazardous and easily accessible biopolymer (tannin) as a carbon precursor, Pluronic F127 surfactant as a pore structuring agent and a palladium salt is reported. This material has the peculiarity to have palladium nanoparticles entrapped in irregular voids connected to the worm-like mesoporous network limiting palladium leaching while keeping good access to the reactants. It was successfully used as a catalyst for ligand-free Suzuki-Miyaura couplings of aryl bromides in a green solvent (propane-1,2-diol) in the presence of extremely low amounts of supported palladium (usually 30 μequiv.). It is noteworthy that almost palladium-free products (containing less than 1.5 μequiv. of precious metal) can be obtained. The possibility to reuse the catalyst was also ascertained.
- Peter, Clovis,Derible, Antoine,Becht, Jean-Michel,Kiener, Julien,Le Drian, Claude,Parmentier, Julien,Fierro, Vanessa,Girleanu, Maria,Ersen, Ovidiu
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supporting information
p. 12297 - 12306
(2015/06/16)
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- Phenylphosphinacalix[3]trifuran: Synthesis, coordination and application in the Suzuki-Miyaura cross-coupling reaction in water
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Phenylphosphinacalix[3]trifuran and supramolecular assemblies with palladium have been synthesized. Phenylphosphinacalix[3]trifuran affords turnover numbers as high as 3.05 × 107 in Suzuki-Miyaura cross-coupling reactions in pure water.
- Sun, Yue,Yan, Meng-Qi,Liu, Yan,Lian, Ze-Yu,Meng, Tong,Liu, Sheng-Hua,Chen, Jian,Yu, Guang-Ao
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p. 71437 - 71440
(2015/09/08)
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- N-heterocyclic carbene-assisted, Bis(phosphine)nickel-catalyzed cross-couplings of diarylborinic acids with aryl chlorides, tosylates, and sulfamates
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Efficient bis(phosphine)nickel-catalyzed cross-couplings of diarylborinic acids with aryl chlorides, tosylates, and sulfamates have been effected with an assistance of N-heterocyclic carbene (NHC) generated in situ from N,N′-dialkylimidazoliums, e.g., N-butyl-N′-methylimidazolium bromide ([Bmim]Br), in toluene using K3PO4·3H2O as base. In contrast to bis(NHC)nickel-catalyzed conventional Suzuki coupling of arylboronic acids, mono(NHC)bis(phosphine)nickel species generated in situ from Ni(PPh3)2Cl2/[Bmim]Br displayed high catalytic activities in the cross-couplings of diarylborinic acids. The structural influences from diarylborinic acids were found to be rather small, while electronic factors from aryl chlorides, tosylates, and sulfamates affected the couplings remarkably. The couplings of electronically activated aryl chlorides, tosylates, and sulfamates could be efficiently effected with 1.5 mol % NiCl2(PPh3)2/[Bmim]Br as catalyst precursor to give the biaryl products in excellent yields, while 3-5 mol % loadings had to be used for the couplings of non- and deactivated ones. A small ortho-substitutent on the aromatic ring of aryl chlorides, tosylates, and sulfamates was tolerable. Applicability of the nickel-catalyzed cross-couplings in practical synthesis of fine chemicals has been demonstrated in process development for a third-generation topical retinoid, Adapalene.
- Ke, Haihua,Chen, Xiaofeng,Zou, Gang
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p. 7132 - 7140
(2014/08/18)
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- Highly efficient nickel/phosphine catalyzed cross-couplings of diarylborinic acids with aryl tosylates and sulfamates
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Highly efficient cross-couplings of diarylborinic acids with aryl tosylates and sulfamates are reported for construction of biaryls using a tri(4-methoxyphenyl)phosphine-supported nickel catalyst system: Ni[P(4-MeOC 6H4)3]2Cl2/2P(4-MeOC 6H4)3 in the presence of K3PO 4·3H2O in toluene. A variety of unsymmetrical biaryls could be obtained in good to excellent yields with 1.5-3 mol% or 3-5 mol% catalyst loadings for aryl sulfamates and tosylates, respectively. In sharp contrast to the conventional nickel-catalyzed Suzuki coupling with arylboronic acids, arylsulfamates unexpectedly displayed a higher reactivity than the corresponding tosylates in coupling with diarylborinic acids catalyzed by the nickel/phosphine catalyst system.
- Ke, Haihua,Chen, Xiaofeng,Feng, Yuanyuan,Zou, Gang
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p. 1126 - 1131
(2014/08/18)
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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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- Suzuki-Miyaura coupling of aryl sulfonates with arylboronic acids using a morpholine-Pd(OAc)2 catalyst system
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We report a new catalyst system, a morpholine-Pd(OAc)2 complex, for Suzuki-Miyaura coupling of aryl tosylates or mesylates with arylboronic acids to give biaryl compounds. The morpholine-Pd(OAc)2 catalyst system is proposed to be a precursor of the catalytically active species in the coupling reaction. Aryl chlorides and aryl triflates can also be used in this coupling reaction. Altogether, 22 biaryl compounds were obtained using this catalyst system. We report a new catalyst system, a morpholine-Pd(OAc) 2 complex, for Suzuki-Miyaura coupling of aryl tosylates or mesylates with arylboronic acids to give biaryl compounds. The morpholine-Pd(OAc) 2 catalyst system is proposed to be a precursor of the catalytically active species in the coupling reaction. Copyright
- Abe, Taichi,Mino, Takashi,Watanabe, Kohei,Yagishita, Fumitoshi,Sakamoto, Masami
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p. 3909 - 3916
(2014/06/24)
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- Water-soluble ionic palladium complexes: Effect of pendant ionic groups on palladium nanoparticles and Suzuki-Miyaura reaction in neat water
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Three ionic nitrogen-containing chelating ligands (L1-L3) are synthesized readily through alkylation and quaternization of 2,2′-dipyridylamine. The charge distributions and natural bond orbital analyses of their cations are implemented by using density functional theory calculations. The catalytic performances of their water-soluble palladium complexes are evaluated preliminarily by using the Suzuki-Miyaura cross-coupling reaction, and high catalytic activities of aryl bromides and chlorides are achieved in neat water. The mercury drop test, poison experiments, and TEM analysis are used to demonstrate the formation of palladium nanoparticles (NPs) after the catalytic reaction. The effects of pendant ionic groups in L1-L3 on the catalytic activities and structures of the palladium NPs are disclosed. These NPs are stable in water for several weeks; they are stabilized by synergetic interactions between the chelating coordination of the 2,2′-dipyridylamino group to the surface of the palladium NPs and the electrostatic repulsion of the ionic groups in L1-L3. Copyright
- Li, Liuyi,Wu, Tao,Wang, Jinyun,Wang, Ruihu
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p. 257 - 265
(2014/03/21)
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- Melamine and melamine-formaldehyde polymers as ligands for palladium and application to Suzuki-Miyaura cross-coupling reactions in sustainable solvents
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The Suzuki-Miyaura cross-coupling reaction is a foundation stone of modern organic synthesis, as evidenced by its widespread use in the preparation of pharmaceuticals, agrochemicals, polymers, and other functional materials. With the prevalence of this venerable reaction in industrial synthesis, it is prudent to ensure its application adheres to the tenets of green chemistry. The introduction of cross-coupling catalysts that are active in sustainable solvents is therefore an important endeavor. In this report, a melamine-palladium complex is introduced as a versatile catalyst for the Suzuki-Miyaura cross-coupling reaction. This catalyst is soluble and active in both water and the renewable organic solvent ethyl lactate. The melamine-palladium catalyst can also be cross-linked by reaction with formaldehyde to generate an insoluble polymeric catalyst that can be recovered after the cross-coupling. The melamine-palladium system is inexpensive, easy to handle, bench-stable, and effective in catalysis in the presence of a variety of impurities (high cross-coupling yields were obtained in reactions run in unfiltered river water to illustrate this final point). Additionally, investigations reported herein revealed an intriguing relationship between catalytic efficiency and the base employed in the cross-coupling reaction. Implications for the mechanism of transmetalation in aqueous Suzuki-Miyaura cross-coupling reaction are discussed.
- Edwards, Grant A.,Trafford, Mitchell A.,Hamilton, Alaina E.,Buxton, Audrey M.,Bardeaux, Matthew C.,Chalker, Justin M.
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p. 2094 - 2104
(2014/04/03)
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- Urea-based porous organic frameworks: Effective supports for catalysis in neat water
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Two urea-based porous organic frameworks, UOF-1 and UOF-2, were synthesized through a urea-forming condensation of 1,3,5-benzenetriisocyanate with 1,4-diaminobenzene and benzidine, respectively. UOF-1 and UOF-2 possess good hydrophilic properties and high scavenging ability for palladium. Their palladium polymers, PdII/UOF-1 and PdII/UOF-2, exhibit high catalytic activity and selectivity for Suzuki-Miyaura cross-coupling reactions and selective reduction of nitroarenes in water. The catalytic reactions can be efficiently performed at room temperature. Palladium nanoparticles with narrow size distribution were formed after the catalytic reaction and were well dispersed in UOF-1 and UOF-2. XPS analysis confirmed the coordination of the urea oxygen atom with palladium. SEM and TEM images showed that the original network morphology of UOF-1 and UOF-2 was maintained after palladium loading and catalytic reactions. Feeling supportive? Two urea-based porous organic frameworks were prepared by a facile urea-forming condensation and can serve as effective supports in palladium-catalyzed Suzuki-Miyaura cross-coupling reactions and reduction of nitroarenes in water. The reactions can even be efficiently performed at room temperature. The original morphology of the urea-based frameworks was maintained after the catalytic reactions.
- Li, Liuyi,Chen, Zhilin,Zhong, Hong,Wang, Ruihu
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p. 3050 - 3060
(2014/03/21)
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- A palladium catalyst supported on carbon-coated cobalt nanoparticles-preparation of palladium-free biaryls by suzuki-miyaura reactions in ethanol
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The preparation of a heterogeneous Pd catalyst supported on carbon-coated magnetic nanoparticles (NPs) bearing 4-(diphenylphosphinomethyl)phenyl groups is discussed. These NPs were initially prepared by chemical vapour deposition (CVD) of carbon on prefor
- Derible, Antoine,Diebold, Carine,Dentzer, Joseph,Gadiou, Roger,Becht, Jean-Michel,Le Drian, Claude
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supporting information
p. 7699 - 7706
(2015/04/22)
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- Suzuki-Miyaura reactions promoted by a PdCl2/sulfonate-tagged phenanthroline precatalyst in water
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This work reports Suzuki-Miyaura cross-coupling reactions of arylboronic acid with aryl halide or aryl dibromide mediated by PdCl2 (0.05mol%) and sodium 4-(1H-imidazo[4,5-f][1,10]phenanthrolin-1-yl)butane-1-sulfonate (0.05mol%) at 100°C in water. The corresponding cross-coupling products were obtained in good to excellent yields. The catalytic system was recovered from the organic products by extraction with ether and the residual aqueous catalyst phase showed high activity after reuse of at least four cycles.
- Li, Qi,Zhang, Li-Ming,Bao, Jia-Jing,Li, Hong-Xi,Xie, Jing-Bo,Lang, Jian-Ping
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p. 861 - 867
(2015/02/05)
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- A general catalyst for Suzuki-Miyaura and Sonogashira reactions of aryl and heteroaryl chlorides in water
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We report the synthesis of 2-(3-sulfonatomesityl)-5-sulfonatoindenyl) dicyclohexylphosphine hydrate sodium salt and its use in palladium-catalyzed Suzuki-Miyaura and Sonogashira coupling reactions in water (and biphasic water-organic solvent mixtures) to prepare a variety of functionalized biaryls and aryl alkynes in excellent yield. This journal is the Partner Organisations 2014.
- Peng, Hui,Chen, Ya-Qin,Mao, Shu-Lan,Pi, Yun-Xiao,Chen, You,Lian, Ze-Yu,Meng, Tong,Liu, Sheng-Hua,Yu, Guang-Ao
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supporting information
p. 6944 - 6952
(2014/09/29)
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- N-Heterocyclic carbene/phosphite synergistically assisted Pd/C-catalyzed Suzuki coupling of aryl chlorides
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An N-heterocyclic carbene and phosphite synergistically enhanced Pd/C catalyst system has been developed for Suzuki coupling of aryl chlorides and aryl boronic acids from commercially available Pd/C with sterically demanding N,N′-bis(2,6-diisopropylphenyl)imidazolylidene and trimethylphosphite. A remarkable increase in catalytic activity of Pd/C was observed when used along with 1 equiv. N,N′-bis(2,6-diisopropylphenyl)imidazolium chloride and 2 equiv. phosphite with respect to palladium in appropriate solvents that were found to play a crucial role in Pd/C-NHC-P(OR)3-catalyzed Suzuki coupling. A dramatic ortho-substitution effect of carbonyl and nitrile groups in aryl chlorides was observed and explained by a modified quasi-heterogeneous catalysis mechanism. The Pd/C catalyst could be easily recovered from reaction mixtures by simple filtration and only low palladium contamination was detected in the biparyl products. A practical process for the synthesis of 4-biphenylcarbonitrile has therefore been developed using the N-heterocyclic carbene/phosphite-assisted Pd/C-catalyzed Suzuki coupling. Copyright
- Ke, Haihua,Chen, Xiaofeng,Zou, Gang
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- Water-soluble palladium click chelating complex: An efficient and reusable precatalyst for Suzuki-Miyaura and Hiyama reactions in water
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A water-soluble ionic palladium(II) nitrogen-containing chelating complex, [palladium(II) 1-(4-N,N′,N′′-trimethylbutylammonium)-4-(2- pyridyl)-1H-1,2,3-triazole dichloride] chloride (3), was prepared through the click reaction of 1-chloro-4-bromobutane, sodium azide, and 2-ethynylpyridine, followed by the quarternization of Me3N and subsequent reaction with [Pd(cod)Cl2] (cod=1,5-cyclooctadiene). The catalytic performances of complex 3 were preliminarily evaluated through Suzuki-Miyaura and Hiyama cross-coupling reactions of aryl bromides; excellent catalytic activity in water was observed. TEM analysis revealed that small palladium nanoparticles (NPs) with a narrow size distribution were formed after the catalytic reaction. The NPs were stabilized by the synergetic effect of coordination and electrostatic interactions from the ionic, bidentate, nitrogen-containing ligand; no palladium black was detected after the aqueous solution of palladium NPs was stored in air for months. The use of 3 as a precursor in the formation of palladium NPs was further explored by using NaBH4 and hydrogen as reductive reagents. The resulting NPs displayed different sizes, surface properties, and catalytic performances in the Suzuki-Miyaura cross-coupling reaction in water. Copyright
- Kong, Fanzhen,Zhou, Chunshan,Wang, Jinyun,Yu, Zhangyu,Wang, Ruihu
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p. 536 - 545
(2013/07/26)
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- Preparation of a titania-supported highly dispersed palladium nano-catalyst and its application in Suzuki and Heck coupling reactions
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In this work, palladium complexes nanoparticles in titania are prepared by a pH-controlled adsorption and without pH-controlled adsorption method. This method results in high-dispersion palladium on the titania surface. We demonstrate the use of the titania-supported palladium as an efficient catalyst for Suzuki and Heck reactions of a representative range of aryl bromides and chlorides. The reusability of catalyst was tested, and deactivation process of the catalyst was not observed after four recycles. The catalysts were characterized by FT-IR, NMR, elemental analysis, field emission scanning electron microscopy, transmission electron microscopy and X-ray diffraction. Copyright
- Karami, Kazem,Shehni, Mahlagha Bahrami,Rahimi, Nasser
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p. 437 - 443
(2013/08/23)
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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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- Palladium nanoparticles catalyzed Suzuki cross-coupling reactions in ambient conditions
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An efficient pathway to synthesize biaryls and terphenyls through ligand-free palladium nanoparticles (PdNPs) catalyzed Suzuki cross-coupling reactions has been developed. Mild reaction conditions, high yields of desired products, absence of inert atmosphere and short reaction times are the notable features of this method.
- Mandali, Pavan Kumar,Chand, Dillip Kumar
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- Palladium mediated C-H bond activation of thiosemicarbazones: Catalytic application of organopalladium complexes in C-C and C-N coupling reactions
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Upon reaction with Pd(PPh3)2Cl2 benzaldehyde thiosemicarbazone undergoes a geometrical change around the imine bond and affords a mixed-ligand complex 1, incorporating an NS-coordinated thiosemicarbazone, a triphenylphosphine and a chloride. Similar reactions with benzophenone thiosemicarbazone and acetophenone thiosemicarbazone proceed without any geometrical change to afford complexes 2 and 3 respectively, containing a CNS-coordinated thiosemicarbazone and a triphenylphosphine. Crystal structures of complexes 1, 2 and 3 have been determined. All the complexes display intense absorptions in the visible region. Catalytic activity of complexes 1, 2 and 3 toward Suzuki type C-C coupling reactions has been examined, and all three are found to efficiently activate all types of C-X bonds (X = I, Br, Cl and even F) and bring about the C-C bond formation with high yield. These complexes are also found to catalyze C-N coupling reactions between aryl halides and primary or secondary amines. While all three complexes are found to be efficient catalysts for both C-C and C-N coupling reactions, complex 2 is found to be a better catalyst than the other two complexes.
- Paul, Piyali,Sengupta, Poulami,Bhattacharya, Samaresh
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supporting information
p. 281 - 288
(2013/04/10)
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- Preparation and application of indolyl secondary phosphine oxides in palladium complexes catalyzed Suzuki-Miyaura cross-coupling reaction
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Several new indolyl secondary phosphine oxides (SPOs), C8H 6N-P(O)(H)(tBu) (4a′), MeC8H 5N-P(O)(H)(tBu) (4b′), and PhC8H 5N-P(O)(H)(tBu) (4c′), were prepared from the reactions of corresponding 1H-indoles with PtBuCl2 and hydrolysis followed. Further reaction of 4a′, a tautomeric form of C 8H6N-P(OH)(tBu) (4a), with Pd(COD)Cl 2 yielded a di-palladium complex, [(4a)(4a-H+)Pd(μ-Cl)] 2 (6a). Crystal structures of PhC8H5N-P(Cl) (tBu) (3c), (4c′) and (6a) were determined by single-crystal X-ray diffraction methods. The stability of this type of SPO is presumably caused by the indolyl scaffold. In addition, SPOs are air- and moisture-stable preligands and are advantageous for the purpose of storage. In this work, these SPO ligands were employed in the Suzuki-Miyaura cross-coupling reactions as catalytic precursors. This catalytic condition has been tolerated to a variety of functional groups and the coupling reactions underwent efficiently with the arylbromides and arylchlorides, respectively.
- Chang, Yen-Yu,Hong, Fung-E
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p. 2327 - 2335
(2013/03/29)
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