- A green direct preparation of a magnetic ordered mesoporous carbon catalyst containing Fe-Pd alloys: Application to Suzuki-Miyaura reactions in propane-1,2-diol
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We report here a direct one-pot preparation of a magnetic mesoporous carbon containing Fe-Pd alloys from biosourced tannin as a carbon precursor, the Pluronic F127 surfactant as a pore structuring agent, PdCl2 and Fe(NO3)3. The starting materials are cheap and easily accessible making the synthesis environmentally benign. This catalyst was successfully used for Suzuki-Miyaura reactions in the presence of extremely low amounts of supported Pd (150 μequiv.) in a non-toxic solvent (propane-1,2-diol). The catalyst can be recovered quantitatively by simple application of an external magnetic field and biaryls containing 1.5 μequiv. of Pd (i.e. 1 ppm) are obtained without any additional purification steps.
- Peter,Derible,Parmentier,Le Drian,Becht
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- Synthesis of water soluble Pd-Piperidoimidazolin-2-ylidene complexes and their catalytic activities in neat water
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Through the strategy of water soluble N-heterocyclic carbene (NHC) ligand, Pd-catalyzed reactions were developed in aqueous media. Therefore, four new piperidoimidazolinium salts (1a-d) consisting of sulfonate (a), esther (b, c) and carboxylic acid (d) functionalities and their water-soluble Pd-NHC complexes (2a-d) were synthesized. The new compounds were characterized by elemental analysis, FTIR, TGA, UV–vis and NMR spectroscopy. The catalytic activities of water soluble Pd-NHC complexes (2a-d) were investigated using the Suzuki-Miyaura (S-M) reaction and the reduction of nitroarenes. We found that the water-soluble polar or ionic groups on piperidoimidazolin-2-ylidine had an effect on the catalytic activity. The water-soluble catalyst can be recycled efficiently and reused six times with only a very slight loss of catalytic activity.
- ?ak?r, Sinem,Türkmen, Hayati
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- Extended architectures constructed of thiourea-modified SBA-15 nanoreactor: A versatile new support for the fabrication of palladium pre-catalyst
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We designed and synthesized a novel catalyst consisting of ordered mesoporous silica (SBA-15) functionalized with bis(thiourea) (BTU) linker. The regular and unique pore channels of BTU-SBA-15 ensure proper control of the size and homogeneous distribution of palladium nanoparticles. The physiochemical properties of the hybrid Pd?BTU-SBA-15 pre-catalyst were investigated using various techniques. The proposed catalyst is found to be very active, reusable, stable and scalable, and has excellent reactivity and selectivity for Suzuki and Heck coupling reactions under very mild and sustainable reaction conditions.
- Alamgholiloo, Hassan,Noroozi Pesyan, Nader,Rostamnia, Sadegh
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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 0049-0050
(2020/06/30)
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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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- 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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- 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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- A Bipyridine-Palladium Derivative as General Pre-Catalyst for Cross-Coupling Reactions in Deep Eutectic Solvents
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A versatile and DES-compatible bipyridine palladium complex has been developed as a general pre-catalyst for different cross-coupling reactions (Hiyama, Suzuki-Miyaura, Heck-Mizoroki and Sonogashira) in deep eutectic solvents. Hydrogen bond capacity of the ligand allows to keep the excellent level of results previously obtained in classical organic solvents. Palladium pre-catalyst showed a high catalytic activity for many cross-coupling reactions, demonstrating a great versatility and applicability. Also, this methodology employs sustainable solvents as a reaction medium and highlights the potential of DES as alternative solvents in organometallic catalysis. The catalyst and DES were easily and successfully recycled. The formation of PdNPs in DES has been confirmed by TEM and XPS analysis and their role as catalyst by mercury test. The dynamic coordination of bipyridine-type ligand in the palladium complex formation has been studied via UV/Vis. (Figure presented.).
- Saavedra, Beatriz,González-Gallardo, Nerea,Meli, Alessandro,Ramón, Diego J.
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supporting information
p. 3868 - 3879
(2019/07/12)
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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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- 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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- Picolinamide modified β-cyclodextrin/Pd (II) complex: Asupramolecular catalyst for Suzuki-Miyaura coupling of aryl, benzyl and allyl halides with arylboronic acids in water
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Novel supramolecular catalysts for Suzuki-Miyaura coupling were prepared and characterized by NMR, FT-IR, TEM, XRD, TGA, and XPS. The resulting picolinamide-modified β-cyclodextrin/Pd(II) complex (Pd(II)@PCA-β-CD) showed very efficient catalytic activity for Suzuki-Miyaura coupling of aryl, benzyl, and allyl halides with arylboronic acids in an environmentally benign aqueous solution. Various organic halides including chlorides can produce good to excellent yields with phenyl-boronic acid and a catalytic amount of Pd(II)@PCA-β-CD. This hydro-soluble catalyst was capable of being reused for at least eight runs with only a slight loss of catalytic activity. A putative mechanism of the Pd(II)/Pd(IV) catalytic cycle was also explored and calculated by ab initio QM/MM methods.
- Luo, Kaixiu,Zhang, Lu,Yang, Rui,Jin, Yi,Lin, Jun
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p. 200 - 210
(2018/08/09)
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- An active catalytic system for Suzuki-Miyaura cross-coupling reactions using low levels of palladium loading
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An easily available Pd(OAc)2/(2-(anthracen-9-yl)-1H-inden-3-yl) dicyclohexylphosphine/toluene/iPrOH/water catalytic system was developed, which shows high catalytic activity in the Suzuki-Miyaura cross-coupling reactions of a diverse array of aryl and heteroaryl chlorides with Pd loadings down to 0.01 mol%.
- Yan, Meng-Qi,Yuan, Jia,Lan, Fang,Zeng, Si-Hao,Gao, Meng-Yue,Liu, Sheng-Hua,Chen, Jian,Yu, Guang-Ao
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supporting information
p. 3924 - 3929
(2017/07/10)
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- Thiourea bridged periodic mesoporous organosilica with ultra-small Pd nanoparticles for coupling reactions
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A synthesis of thiourea-bridged mesoporous organosilica is reported. Using transmission electron microscopy, low-angle XRD measurements and N2 adsorption-desorption isotherms the formation of a highly ordered mesoporous structure with a high surface area (>400 m2 g-1) has been confirmed. Deposition of Pd nanoparticles inside the mesopores resulted in a material that showed excellent catalytic activity in a Suzuki-coupling reaction and retained this activity over several consecutive runs.
- Doustkhah, Esmail,Rostamnia, Sadegh,Imura, Masataka,Ide, Yusuke,Mohammadi, Shiva,Hyland, Christopher J. T.,You, Jungmok,Tsunoji, Nao,Zeynizadeh, Behzad,Yamauchi, Yusuke
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p. 56306 - 56310
(2017/12/26)
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- Cyclodextrin-supported palladium complex: A highly active and recoverable catalyst for Suzuki–Miyaura cross-coupling reaction in aqueous medium
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A water-soluble, cyclodextrin-supported palladium complex (DACH-Pd-β-CD) catalytic system was designed and synthesized, which can efficiently catalyze Suzuki–Miyaura cross-coupling reactions between aryl halides and arylboronic acid in water under mild conditions. The catalyst was successfully characterized using the methods of transmission electron microscopy, energy-dispersive X-ray spectrometry, X-ray diffraction, thermogravimetric analysis, and Fourier transform infrared and NMR spectroscopies. Furthermore, the catalyst can be easily separated from the reaction mixture and still maintain high catalytic activity after ten cycles. No leaching of palladium into the reaction solution occurred. The advantages of green solvent (water), short reaction times (2–6?h), low catalyst loading (0.001?mol%), excellent yields (up to 99%) and reusability of the catalyst mean it will have potential applications in green chemical synthesis.
- Guo, Yafei,Li, Jiuling,Shi, Xiwei,Liu, Yang,Xie, Kai,Liu, Yuqi,Jiang, Yubo,Yang, Bo,Yang, Rui
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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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- 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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- 2-Aryl-indenylphosphine ligands: Design, synthesis and application in Pd-catalyzed Suzuki-Miyaura coupling reactions
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A focused library of phosphine ligands was constructed for structural optimization. The catalyst can be used to perform the Suzuki-Miyaura cross-coupling reaction of aryl and heteroaryl chlorides.
- Lian, Ze-Yu,Yuan, Jia,Yan, Meng-Qi,Liu, Yan,Luo, Xue,Wu, Qing-Guo,Liu, Sheng-Hua,Chen, Jian,Zhu, Xiao-Lei,Yu, Guang-Ao
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supporting information
p. 10090 - 10094
(2016/11/06)
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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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- 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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- 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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- 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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- 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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- 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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- 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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- Pd(OAc)2@SBA-15/PrEn nanoreactor: A highly active, reusable and selective phosphine-free catalyst for Suzuki-Miyaura cross-coupling reaction in aqueous media
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A series of ordered mesoporous organic-inorganic hybrid material was designed by using the amine-functionalized SBA-15 (PdX2@SBA-15/N Y, Y = 1, 2) as solid support for palladium complexes. Among them, the Pd(OAc)2/ethylenediamine complex encapsulated into SBA-15 (Pd(OAc)2@SBA-15/PrEn or Pd(OAc)2@SBA-15/PrNHEtNH 2) exhibits higher activity and selectivity toward Suzuki cross-coupling reaction under aerobic conditions and water solvent mixture. The SBA-15/PrEn supported palladium pre-catalyst could be separated easily from reaction products and used repetitively several times, showing its superiority over homogeneous catalysts for industrial and chemical applications. Copyright
- Rostamnia, Sadegh,Xin, Hongchuan
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p. 348 - 352
(2013/07/28)
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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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- Palladium nanoparticle catalysis: Borylation of aryl and benzyl halides and one-pot biaryl synthesis via sequential borylation-Suzuki-Miyaura coupling
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Palladium nanoparticles generated in PEG catalyze the reaction of bis(pinacolato)diboron with various aryl/benzyl halides to afford aryl/benzyl boronates in high yield. Arylboronates thus prepared, have been directly used in the Suzuki-Miyaura coupling reaction with different aryl halides and benzyl halides in a convenient one-pot, two-step solvent free green synthesis of unsymmetrical biaryls and diarylmethanes. The Royal Society of Chemistry 2012.
- Bej, Ansuman,Srimani, Dipankar,Sarkar, Amitabha
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experimental part
p. 661 - 667
(2012/05/04)
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- PH-Responsive chelating N-heterocyclic dicarbene palladium(ii) complexes: Recoverable precatalysts for Suzuki-Miyaura reaction in pure water
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A hydrophobic palladium complex of the chelating N-heterocyclic dicarbene (NHDC) (3) was synthesized through in situ deprotonation of a bisimidazolium salt (2) by Pd(OAc)2 in DMSO, subsequent basic hydrolysis and acidification resulted in the formation of four NHDC palladium complexes bearing carboxylic functional groups (4-7). Complexes 4-7 are air-stable, pH-responsive and water-soluble under basic conditions due to deprotonation of the carboxylic groups. The catalytic activities of the hydrophilic catalytic systems from 4-7 were preliminarily evaluated using the Suzuki-Miyaura cross-coupling reaction in pure water, high catalytic activity and chemical selectivity were observed in comparison with their hydrophobic analogue from 3. Either the catalytic aqueous solution or the pH-responsive catalysts were easily separated and could be recycled at least four times. TEM analysis revealed that Pd(0) nanoparticles were formed after the catalytic reaction.
- Li, Liuyi,Wang, Jinyun,Zhou, Chunshan,Wang, Ruihu,Hong, Maochun
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experimental part
p. 2071 - 2077
(2011/09/16)
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- A palladium chelating complex of ionic water-soluble nitrogen-containing ligand: The efficient precatalyst for Suzuki-Miyaura reaction in water
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An ammonium-functionalized water-soluble bidentate nitrogen-containing ligand (3) and its palladium chelating complex (4) have been easily prepared from the commercial available starting materials in high overall yields. The charge distributions and molecular orbital analyses of 3, 4 and non-ionic hydrophobic analogue (2a) based on the optimized structures were implemented. The crystal structure of 4 has been established by single-crystal X-ray diffraction. The water-soluble palladium complex was a much more effective catalyst than 2a in palladium-catalyzed Suzuki-Miyaura cross-coupling reaction in air and pure water. High catalytic activity of aryl chlorides and aryl bromides was observed. The mercury drop test, poison experiments and TEM analysis of the catalytic solution showed Pd(0) were involved in catalysis. The palladium nanoparticles of 3.0 ± 0.6 nm were formed after the catalytic reaction, they were stabilized by synergetic effect of coordination and electrostatic interactions from the ammonium-functionalized chelating ligand. No precipitate was observed when the aqueous nanoparticles were stored in air for months.
- Zhou, Chunshan,Wang, Jinyun,Li, Liuyi,Wang, Ruihu,Hong, Maochun
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experimental part
p. 2100 - 2106
(2011/10/03)
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- Cavitand supported tetraphosphine: Cyclodextrin offers a useful platform for Suzuki-Miyaura cross-coupling
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The cyclodextrin-tetraphosphine hybrid coined α-Cytep allows turnover numbers up to 340000000000 and turnover frequencies up to 1000000000 h -1 to be reached in Suzuki-Miyaura reactions. These exceptional figures are clearly linked to the outst
- Zaborova, Elena,Deschamp, Julia,Guieu, Samuel,Bleriot, Yves,Poli, Giovanni,Menand, Mickael,Madec, David,Prestat, Guillaume,Sollogoub, Matthieu
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supporting information; experimental part
p. 9206 - 9208
(2011/10/01)
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- Pd-catalyzed coupling of aryl iodides with triarylbismuths as atom-economic multi-coupling organometallic nucleophiles under mild conditions
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The facile cross-coupling reactivity of triarylbismuth compounds with aryl iodides was achieved under mild heating conditions. The established catalytic protocol using Pd(OAc)2(Cy2NH)2 system exhibited high coupling reactivity with a variety of triarylbismuth and aryl iodide compounds under mild conditions. These coupling reactions were completed in short reaction time affording good to high yields of functionalized biaryl products. The studies of multi-coupling reactions with tris(4-iodophenyl)amine, 8 also furnished moderate to good yields of coupled products, 8a-8f.
- Rao, Maddali L.N.,Banerjee, Debasis,Dhanorkar, Ritesh J.
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supporting information; experimental part
p. 6101 - 6104
(2011/01/04)
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- A robust hydrophilic pyridine-bridged bis-benzimidazolylidene palladium pincer complex: Synthesis and its catalytic application towards Suzuki-Miyaura couplings in aqueous solvents
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A novel hydrophilic pyridine-bridged bis-benzimidazolylidene palladium pincer complex (3) acted as a highly efficient robust recyclable molecular catalyst towards Suzuki-Miyaura coupling reactions in aqueous media and tolerated various functional groups (even heterocycles) with extremely low catalyst loading. The Royal Society of Chemistry 2010.
- Tu, Tao,Feng, Xike,Wang, Zhixun,Liu, Xiyu
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supporting information; experimental part
p. 10598 - 10600
(2011/01/10)
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- Canopied trans-chelating bis(N-heterocyclic carbene) ligand: Synthesis, structure and catalysis
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The terphspan scaffold was employed to support a bis(N-heterocyclic carbene) ligand (1) that provides a m-terphenyl canopy over one side of its metal complexes. Single-crystal X-ray diffraction studies on a silver complex of {[Ag(1)]AgBr2}2 revealed an unusual tetranuclear silver core with a Ag-Ag bond distance of 3.0241(8) with 1 as a trans-chelating ligand (C-Ag-C = 171°). A preliminary X-ray structure of pseudo-square planar [PdCl2(1)] showed a similar binding mode of 1 (C-Pd-C = 177°). High yields were obtained in Suzuki-Miyaura coupling reactions utilizing [PdCl2(1)] as the procatalyst and the results were compared with analogous complexes of trans-spanning diphosphine (2) and diphosphinite (3) complexes. The diphosphinite complex, [PdCl2(3)], decomposes to [μ-ClPd(PPh2OH)(PPh2O)]2 at room temperature. The Royal Society of Chemistry 2009.
- Morgan, Brad P.,Galdamez, Gabriela A.,Gilliard Jr., Robert J.,Smith, Rhett C.
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experimental part
p. 2020 - 2028
(2009/05/15)
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- N-heterocyclic carbene derived Nickel-Pincer complexes: Efficient and applicable catalysts for Suzuki-Miyaura coupling reactions of aryl/alkenyl tosylates and mesylates
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Catalytic activities of NHC-derived nickel-pincer complexes for the Suzuki-Miyaura coupling reactions of aryl/alkenyl to- sylates and mesylates are described. In the presence of a catalytic amount of nickelacycle 1a, a wide array of tosylates and mesylates reacted with several aryl- and alkenylboronic acids to afford the coupling products, generally in high yields. Fine tuning of the reaction conditions for each class of electrophiles was achieved only by choosing the appropriate reaction medium (DME for tosylates, dioxane for mesylates).
- Kuroda, Jun-Ichi,Inamoto, Kiyofumi,Hiroya, Kou,Doi, Takayuki
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experimental part
p. 2251 - 2261
(2009/08/09)
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- Shape-dependent catalytic activity of copper oxide-supported Pd(0) nanoparticles for Suzuki and cyanation reactions
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Palladium nanoparticles supported on different shapes of nanocrystalline CuO are prepared by the treatment of Cu(NO3)2 and Pd(OAc)2 in polyethylene glycol (PEG-6000). The shapes of the CuO/Pd composite are dependent on the amount of PEG used. Suzuki coupling was catalyzed efficiently by the oval-shaped material, whereas the rod shape facilitates the cyanation reaction. The CuO/Pd catalyst is recovered and reused for subsequent Suzuki reactions; however, cyanation poisons the catalyst for further use. Both these reactions are very clean and high yielding.
- Chattopadhyay, Kalicharan,Dey, Raju,Ranu, Brindaban C.
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supporting information; experimental part
p. 3164 - 3167
(2009/08/09)
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- Naphthidine di(radical cation)s-stabilized palladium nanoparticles for efficient catalytic Suzuki-Miyaura cross-coupling reactions
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Stable Pd(0) nanoparticles were prepared at room temperature in 1,4-dioxane from PdCl2 using N,N′-bis(4-methoxyphenyl)-(1,1′-binaphthyl)-4,4′-diamine (naphthidine) as reducing and stabilizing agent. This procedure resulted in Pd(0) particles possessing an average diameter of ca. 25 nm stabilized against aggregation due to a barrier of the naphthidine di(radical cation) Napht2.2+. These particles were evaluated for their capability to act as catalysts in Suzuki-Miyaura coupling reactions. The Pd(0)/Napht2.2+ provides a general and convenient method to prepare biaryls from aryl bromides or iodides and boronic acids with a broad range of functional groups in 1,4-dioxane at 80 °C and under aerobic conditions.
- Desmarets, Christophe,Omar-Amrani, Rafik,Walcarius, Alain,Lambert, Jacques,Champagne, Beno?t,Fort, Yves,Schneider, Rapha?l
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p. 372 - 381
(2008/04/01)
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- Suzuki coupling catalyzed by a homoleptic Pd(I)-Pd(I) solvento complex
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The PdI-PdI bonded complex [Pd2(CH3CN)6][SbF6] 2 is catalytically active towards Suzuki cross-coupling reactions of aryl bromides or chlorides with various arylboronic acids under mild conditions giving good to excellent yields. Its performance is enhanced by the introduction of stoichiometric or limited phosphines. The effects of different ligands, metal oxidation states [Pd(II), Pd(I) Pd(0)], bases and solvents have been examined.
- Han, Xiaoyan,Weng, Zhiqiang,Hor, T. S. Andy
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p. 5690 - 5696
(2008/03/13)
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- Ligands for metals and improved metal-catalyzed processes based thereon
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One aspect of the present invention relates to ligands for transition metals. A second aspect of the present invention relates to the use of catalysts comprising these ligands in transition metal-catalyzed carbon-heteroatom and carbon-carbon bond-forming reactions. The subject methods provide improvements in many features of the transition metal-catalyzed reactions, including the range of suitable substrates, reaction conditions, and efficiency.
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- Ligands for metals and improved metal-catalyzed processes based thereon
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One aspect of the present invention relates to novel ligands for transition metals. A second aspect of the present invention relates to the use of catalysts comprising these ligands in transition metal-catalyzed carbon-heteroatom and carbon-carbon bond-forming reactions. The subject methods provide improvements in many features of the transition metal-catalyzed reactions, including the range of suitable substrates, reaction conditions, and efficiency.
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- Formation Constants of Cyanohydrins of Substituted Acetylbiphenyls
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The formation constants of cyanohydrins of 2'- and 3'-substituted 4-acetylbiphenyls have been determined at 30 deg C in 80percent dioxan-water (v/v).The 3'-substituted 4-acetylbiphenyls obey the Hammett equation giving a ρ-value of 0.52; 2'-substituted cyanohydrins do not obey the Hammett equation.The formation constants of 3'-substituted 4-acetylbiphenyls and their rate constants for the reduction by sodium borohydride reveal a linear relationship (r = 0.990).The influence of 2'-substituents reveals the existence of ?-electron steric effect.
- Ananthakrishnanadar, P.,Kannan, N.
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