- A crosslinked bis(amino)-containing polymer as a remarkable support for heterogeneous palladium-catalyzed Suzuki-Miyaura reaction
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Through the substitution reaction of hexachlorocyclotriphosphazene (HCCP) and 4,4′-diaminobiphenyl (DABP), a crosslinked polymer HCCP-DABP was synthesized by a conventional and convenient route. Owing to the strong coordination ability of pincer-type bis(amino) scaffold in the matrix, the polymer was successfully used as a support to form stable palladium catalyst complex Pd/HCCP-DABP. The palladium catalyst showed excellent reactivity in Suzuki-Miyaura cross-coupling reaction. In addition, the catalyst can be readily recovered and reused for further transformations at least 10 times without significant decrease in catalytic activity.
- Wang, Yiming,Lu, Cuifen,Yang, Guichun,Chen, Zuxing,Nie, Junqi
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- A highly recoverable polymer-supported ionic salen-palladium complex as a catalyst for the Suzuki-Miyaura cross coupling in neat water
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A polymer supported Pd-salen complex (PS-Pd-salen) was synthesized and characterized by Fourier transform infrared spectroscopy (FT-IR), Fourier-transform NMR spectroscopy (FT-NMR), thermal gravimetric analysis (TGA), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), surface area and pore size distribution by Brunauer-Emmett-Teller (BET). The heterogeneous catalytic performance of the PS-Pd-salen for the Suzuki-Miyaura coupling of variety of phenyl boronic acid with different aryl halides was successfully conducted in water with K2CO3 and 20 mg catalyst loading at room temperature. The coupling reactions with aryl iodides and bromides were achieved at room temperature with good to excellent yield; whereas the reactions with aryl chlorides were performed in aqueous-ethanol (1:1) at 90 °C. The product yields related with the substrates were optimized, and main reaction factors influencing the yields were also recognized. The results clearly indicated that the reaction constraints needed to achieve high yields are substrate-reliant. The hot filtration test verified heterogeneous nature of PS-Pd-salen complex. Moreover, the catalyst showed excellent reusability for five successive runs in slight compromising with its activity.
- Balinge, Kamlesh Rudreshwar,Khiratkar, Avinash Ganesh,Bhagat, Pundlik Rambhau
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- A green synthesis of palladium nanoparticles by Sapindus mukorossi seed extract and use in efficient room temperature Suzuki–Miyaura cross-coupling reaction
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A simple and green method for the synthesis of palladium nanoparticles using an aqueous extract of Sapindus mukorossi seed has been demonstrated. The synthesized nanoparticles were characterized using UV–visible spectroscopy, powxder X-ray diffraction, energy-dispersive X-ray analysis and transmission electron microscopy. The nanocatalyst was successfully utilized in an efficient Suzuki–Miyaura cross-coupling reaction at room temperature.
- Borah, Raju Kumar,Mahanta, Abhijit,Dutta, Anurag,Bora, Utpal,Thakur, Ashim J.
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- Pd nanoparticles immobilized on PNIPAM-halloysite: Highly active and reusable catalyst for Suzuki-Miyaura coupling reactions in water
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Poly(N-isopropylacrylamide)-halloysite (PNIPAM-HNT) nanocomposites exhibited inverse temperature solubility with a lower critical solution temperature (LCST) in water. Palladium (Pd) nanoparticles were anchored on PNIPAM-HNT nanocomposites with various amounts of HNT from 5 to 30 wt%. These Pd catalysts exhibited excellent reactivities for Suzuki-Miyaura coupling reactions at 50-70 °C in water. In particular, Pd anchored PNIPAM/HNT (95:5 w/w ratio) nanocomposites showed excellent recyclability up to 10 times in 96% average yield by simple filtration. Copyright
- Hong, Myeng Chan,Ahn, Hyunseok,Choi, Myung Chan,Lee, Yongwoo,Kim, Jongsik,Rhee, Hakjune
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- Pd nanoparticles as efficient catalysts for Suzuki and Stille coupling reactions of aryl halides in ionic liquids
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Pd-catalyzed Suzuki and Stille cross-couplings of aryl bromides and chlorides were carried out in quaternary ammonium salts as solvents under mild conditions and with the recycling of the catalyst.
- Calo, Vincenzo,Nacci, Angelo,Monopoli, Antonio,Montingelli, Floriana
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- Trans -chloro(1-naphthyl)bis(triphenylphosphine)nickel(II)/PCy3 catalyzed cross-coupling of aryl and heteroaryl neopentylglycolboronates with aryl and heteroaryl mesylates and sulfamates at room temperature
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trans-Chloro(1-naphthyl)bis(triphenylphosphine)nickel(II) complex/PCy 3 system has been successfully applied as catalyst for the Suzuki-Miyaura cross-coupling of aryl and heteroaryl neopentylglycolboronates with aryl and heteroaryl mesylates and sulfamates in THF at room temperature. This cross-coupling reaction tolerates various functional groups, including keto, imino, ester, ether, and cyano. Together with the nickel-catalyzed, one-pot, two-step neopentylglycolborylation, this bench stable and inexpensive Ni(II)-based catalyst can be utilized as an alternative to Ni(COD) 2/PCy3 to provide an inexpensive, robust, and convenient synthesis of biaryl and heterobiaryl compounds.
- Leowanawat, Pawaret,Zhang, Na,Safi, Mehtap,Hoffman, David J.,Fryberger, Miriam C.,George, Aiswaria,Percec, Virgil
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- Efficient protocol for the phosphine-free Suzuki-Miyaura reaction catalyzed by palladium on carbon at room temperature
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A mild and efficient protocol for the phosphine-free Suzuki-Miyaura coupling reaction of aryl bromides with arylboronic acids has been developed which utilizes the commercially available 10% Pd/C (3.5 mol% Pd) in ethanol-water (1:1) and Na2CO3 at room temperature. The reaction is convenient, environmentally benign and generates excellent yields of the coupled products (94-100%). The catalyst can be recycled using simple filtration and washing sequences without significant decrease in the yield of coupling product up to the fourth run.
- Zhang, Guolin
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- Air-stable imidazole-imine palladium complexes for Suzuki-Miyaura coupling: Toward an efficient, green synthesis of biaryl compounds
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New imidazole-imine ligands have been developed for the air and moisture stable Pd-catalyzed Suzuki-Miyaura cross-coupling reaction. Under optimized reaction conditions, coupling products from a wide range of aryl halides and aryl boronic acids were obtained in excellent yields.
- Ratniyom, Jadsada,Chaiprasert, Thanawat,Pramjit, Songyos,Yotphan, Sirilata,Sangtrirutnugul, Preeyanuch,Srisuratsiri, Pailin,Kongsaeree, Palangpon,Kiatisevi, Supavadee
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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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- Pd/MOF-199: As an efficient heterogeneous catalyst for the Suzukie Miyaura cross-coupling reaction
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Successful deposition of Pd nanoparticles is described using MOF-199 as a support. Various characterization techniques including FTIR, XRD, SEM, BET-BJH, TG-DTA, and NH3-TPD were used to verify the efficiency of catalysts. Pd/MOF-199 is utilized as a catalyst for Suzukie Miyaura reactions with reasonable to excellent reaction yields under reflux conditions in H2O: ethanol solvent.
- Sanaei, Mehran,Fazaeli, Razieh,Aliyan, Hamid
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- Palladium catalyzed atom-efficient cross-coupling reactions of triarylbismuths with aryl bromides
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Aryl bromides (3 equiv) were coupled efficiently with triarylbismuths (1 equiv) in an atom-efficient way using the Pd(OAc)2/PPh3 catalytic system in the presence of K3PO4 as base in DMF at 90 °C, providing excellent yields of the cross-coupled biaryls in short reaction times.
- Rao, Maddali L.N.,Banerjee, Debasis,Jadhav, Deepak N.
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- CNC pincer palladium complex supported on magnetic chitosan as highly efficient and recyclable nanocatalyst in C─C coupling reactions
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A stable and durable magnetic chitosan-supported triazine-bridged bisimidazolium pincer palladium catalyst (Fe3O4@ChC@CNC-PdII) was synthesized and characterized using various techniques. The Fe3O4@ChC@CNC-PdII complex displayed high activity in the production of substituted biaryls via the cross-coupling reactions of aryl halides with arylboronic acids. Also, this catalyst could be simply recovered from the reaction mixture and reused in 13 consecutive runs with no loss of its catalytic activity.
- Rafiee, Fatemeh,Hosseini, S. Azam
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- An immobilized symmetrical bis-(NHC) palladium complex as a highly efficient and recyclable Suzuki-Miyaura catalyst in aerobic aqueous media
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A bis-N-heterocyclic carbene (NHC) functionalized with chloropropyltriethoxysilane over silica was used to synthesize a well-defined immobilized palladium complex. This complex is a suitable and easily retrievable catalyst for Suzuki-Miyaura cross-coupling reactions under mild aqueous conditions. Excellent yields and conversions were obtained with low palladium loadings (down to 0.03 mol% Pd). The catalyst can be reused up to six cycles without the loss of its activity. The catalytic role of the NHC complex of palladium during coupling between bromobenzene and phenylboronic acid was investigated theoretically. The oxidative addition step is predicted to be endothermic in agreement with the experimental conditions.
- Begum, Tahshina,Mondal, Manoj,Borpuzari, Manash Protim,Kar, Rahul,Kalita, Golap,Gogoi, Pradip K.,Bora, Utpal
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- A robust method for the Hiyama-type coupling of arylsiloxanes and disiloxanes with aryl halides
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Palladium catalysed Hiyama-type coupling of aryl disiloxanes or aryl silanols with aryl halides in the presence of stoichiometric silver(I) oxide and catalytic TBAF allows the rapid preparation of biaryls in moderate to high yield under mild thermal or microwave irradiation conditions.
- Napier, Spencer,Marcuccio, Sebastian M.,Tye, Heather,Whittaker, Mark
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- Pd(N,N-dimethyl β-alaninate)2 as a high-turnover-number, phosphine-free catalyst for the suzuki reaction
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A novel crystalline, air- and moisture-stable Pd salt, Pd(N,N-dimethyl β-alaninate)2, was synthesized. This salt was demonstrated to constitute a low-priced, phosphine-free, yet high-turnover-number (TON = 10 4) catalyst for the Suzuki reactions of various aryl bromides and iodides under mild and simple reaction conditions. Moreover, it was observed that the presence of an olefin could dramatically hamper the Suzuki reaction. Georg Thieme Verlag Stuttgart.
- Cui, Xin,Qin, Tian,Wang, Jia-Rui,Liu, Lei,Guo, Qing-Xiang
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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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- Fluorous biphasic catalysis without perfluorinated solvents: Application to Pd-Mediated Suzuki and Sonogashira couplings
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With and now without: Perfluoro-tagged catalysts immobilized on fluorous reversed-phase silica gel can be used for Suzuki and Sonogashira C-C coupling reactions (see scheme; R1 = e.g., phenyl, 4-MeOC6H4, R2 e.g., 4-NO2C6H4, 4-MeCOC6H4, X = Br, I) without the need for perfluorinated solvents. After the reaction the products were isolated by decantation and the Pd catalysts were recovered and reused.
- Tzschucke, Carl Christoph,Markert, Christian,Glatz, Heiko,Bannwarth, Willi
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- Suzuki cross-coupling reactions of aryl halides in phosphonium salt ionic liquidunder mild conditions
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The Suzuki cross-coupling of aryl boronic acids with aryl halides, including aryl chlorides, proceeds in the phosphonium salt ionic liquid tetradecyltrihexylphosphonium chloride under mild conditions.
- McNulty, James,Capretta, Alfredo,Wilson, Jeff,Dyck, Jeff,Adjabeng, George,Robertson, Al
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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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- Ultrasound-assisted C-C coupling reactions catalyzed by unique SPION-A-Pd(EDTA) as a robust nanocatalyst
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A novel and highly stable Pd(EDTA)2- salt was synthesized as a catalyst, using a counter-cation of N-methylimidazolium bonded to 1,3,5-triazine-tethered SPIONs (superparamagnetic iron oxide nanoparticles). This well-defined complex efficiently
- Ghotbinejad, Marzieh,Khosropour, Ahmad R.,Mohammadpoor-Baltork, Iraj,Moghadam, Majid,Tangestaninejad, Shahram,Mirkhani, Valiollah
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- Imidazolium-based ionic liquid functionalized reduced graphene oxide supported palladium as a reusable catalyst for Suzuki-Miyaura reactions
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A novel palladium immobilized on reduced graphene oxide heterogeneous catalyst was prepared. The reduced graphene oxide was functionalized by imidazolium-based ionic liquids containing polyethylene glycol monomethyl ether moieties. The prepared catalyst can achieve Suzuki-Miyaura reactions efficiently in green solvents under mild conditions and could be recycled for five catalytic runs without the loss of activity.
- Shi, Xin,Cai, Chun
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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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- Synthesis of Biaryl derivatives via a magnetic Pd-NPs-catalyzed one-pot diazotization-cross-coupling reaction
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A magnetic Pd-NPs-catalyzed one-pot diazotizationcross-coupling reaction of anilines and arylboronic acids was developed. Biaryl derivatives were therefore synthesized in good to excellent yields. Through magnetic separation, the catalyst could be recovered and reused for five times. There were several obvious advantages such as broad applicability, high selectivity, simply experimental operation as well as the convenient preparation, high efficiency and reusability of catalyst. Georg Thieme Verlag Stuttgart ? New York.
- Zong, Yan,Hu, Jiefeng,Sun, Peipei,Jiang, Xiaoqing
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- 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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- Water-promoted Suzuki reaction in room temperature ionic liquids
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The Suzuki reaction was successfully performed by using Pd(OAc)2 as the catalyst in a mixture of water and ionic liquids in a short reaction time in air. Water was found to have a remarkable rate accelerating effect on the Suzuki reaction in ionic liquids. The Pd(OAc)2-[bmim][PF 6] can be reused seven times only with a small deactivation of reactivity. Georg Thieme Verlag Stuttgart.
- Xin, Bingwei,Zhang, Yuhong,Liu, Leifang,Wang, Yanguang
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- Catalytic and stoichiometric reactions of Arylpalladium(II) complexes bearing a trans-chelating dinitrogen ligand with arylboronic acids
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Pd(II) complexes with 1,2-bis(2′-pyridylethylnyl)benzene (bpeb) ligand, PdCl2(bpep) and Pd(OAc)2(bpep), catalyze cross-coupling of arylboronic acids and aryl iodide, in spite of the trans-chelation of the ligand. Arylpalladium iodo and trifluoroacetate complexes with bpep ligand, Pd(C6H4X-4)(I)(bpep) (3a-3h, X = OMe, Me, H, COMe, CHO, COOEt, NO2, F), Pd(C6H3F2-2,4)(I)(bpep) (3i), Pd(C6H4X-4)(OCOCF3)(bpep) (4a-4e, X = OMe, Me, H, COMe, CHO) and Pd(C6F5)(OCOCF3)(bpep) (4j), were obtained by ligand exchange of the Pd complexes having tmeda ligand (tmeda = N,N,N′,N′-tetramethylethylenedi-amine). X-ray crystallographic results of arylpalladium(II) trifluoroacetate complex, Pd(C6H4OMe-4)(OCOCF3)(bpeb) (4a), and bis(trifluoroacetate)palladium(II) complex, Pd(OCOCF3)2(bpeb) (5) revealed the structures with two pyridyl groups of bpeb coordinated to Pd(II) in a trans-chelating bidentate mode. 2-Pyridyl hydrogens and an acetate oxygen of 5 are at close positions to each other (2.52 and 2.66 ?). The reaction of (4-MeC6H4)B(OH)2 (7b) with Pd(C6H4OMe-4)(OCOCF3)(bpeb) (4a) in the presence of Ag2O yields Pd(C6H4Me-4)(OCOCF3)(bpeb) (4b) via exchange of the aryl group between the palladium complex and arylboronic acid. The reaction of (4-CHOC6H4)B(OH)2 (7e) yields not only Pd(C6H4CHO-4)(OCOCF3)(bpeb) (4e) but also biaryls, 4-MeOC6H4-C6H4Y-4 (Y = OMe (8a), CHO (8e)). Hammett plots of the reaction exchange suggest higher reactivity of the Pd complex with more electron-donating aryl ligand.
- Suzaki, Yuji,Saito, Takashi,Osakada, Kohtaro
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- Polymer-supported N-heterocyclic carbene-palladium complex for heterogeneous suzuki cross-coupling reaction
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Poly(1-methylimidazoliummethyl styrene)-surface grafted-poly(styrene) resin was prepared for the first time as a polymer-supported N-heterocyclic carbene (NHC) precursor for palladium complex by suspension polymerization. To prepare this polymer-supported NHC precursor, 1-methyl-3-(4-vinylbenzyl)imidazolium hexafluorophosphate, [MVBIM] [PF6-], was synthesized as a monomer and copolymerized with styrene and DVB in water. This polymer-supported NHC precursor with imidazolium as a ligand, which exists solely on the surface of the resin, was well characterized by FE-SEM, CLSM, and IR spectroscopy. The precursor containing imidazolium readily formed a stable complex with Pd(OAc)2, and this polymer-supported N-heterocyclic carbene-palladium complex exhibited excellent catalytic activity for Suzuki cross-coupling reaction in an aqueous medium. The catalyst was recovered quantitatively from the reaction mixture by simple filtration and was able to be reused for a number of recycles with consistent activity in all of the coupling reactions.
- Kim, Jong-Ho,Kim, Jung-Woo,Shokouhimehr, Mohammadreza,Lee, Yoon-Sik
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- A palladium complex with functionalized β-cyclodextrin: A promising catalyst featuring recognition abilities for Suzuki-Miyaura coupling reactions in water
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A water-soluble palladium complex (PdLnβ-CD) was designed and prepared based on functionalized β-cyclodextrin. It showed high turnover numbers (TONs) and turnover frequencies (TOFs) of up to 9.9 × 108 and 4.9 × 108 h-1, respectively, in aqueous Suzuki-Miyaura coupling reactions. The detailed reason for the excellent catalytic activity was studied.
- Zhang, Guofu,Luan, Yuxin,Han, Xingwang,Wang, Yong,Wen, Xin,Ding, Chengrong,Gao, Jianrong
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- A Polymer-Bound Monodentate-P-Ligated Palladium Complex as a Recyclable Catalyst for the Suzuki-Miyaura Coupling Reaction of Aryl Chlorides
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A three-fold cross-linked polymer-bound phosphine (POL-Ph3P) with high phosphorus content has been prepared. The phosphorus-containing polymer forms a monodentate-P-ligated palladium complex, which shows excellent activity in Suzuki-Miyaura cross-coupling reactions of aryl chlorides. Importantly, the catalyst Pd/POL-Ph3P is highly stable and can be reused for at least 10 times without losing reactivity.
- Zhou, Yun-Bing,Li, Cun-Yao,Lin, Min,Ding, Yun-Jie,Zhan, Zhuang-Ping
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- Non-cross-linked polystyrene-supported triphenylphosphine-microencapsulated palladium: An efficient and recyclable catalyst for Suzuki-Miyaura reactions
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A recyclable, all-in-one, polystyrene-microencapsulated palladium catalyst has been developed and used as a heterogeneous catalyst in Suzuki-Miyaura coupling reactions. This catalyst can be recovered and reused with only minimal palladium leaching observed. Georg Thieme Verlag Stuttgart.
- He, Helen Song,Yan, Jessie Jing,Shen, Ruxiang,Zhuo, Shangjun,Toy, Patrick H.
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- Synthesis of immobilized nanopalladium on polymer-supported Schiff base, and study of its catalytic activity in the Suzuki-Miyaura reaction
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Nanopalladium particles immobilized on a matrix of poly(vinyl chloride) (PVC)-supported Schiff base were prepared from PVC with sequential attachment of ethylenediamine and salicylaldehyde, followed by treatment with an ethanolic solution of palladium chloride. The as-prepared catalyst was found to be air and moisture-stable and to have significant catalytic activity in Suzuki-Miyaura reactions under mild operating conditions. Various phenyl halides were coupled with phenylboronic acid in aqueous ethanol, under air, to afford the corresponding cross-coupled products in good yields. Furthermore, the catalyst can be easily recovered by simple filtration and reused for up to five cycles without losing its activity.
- Liu, Jie,Li, Yi-Qun,Zheng, Wen-Jie
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- Sulfur modification of Au via treatment with piranha solution provides low-pd releasing and recyclable Pd material, SAPd
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We have found in the SR-HXPS measurement of Piranha-treated Au(111)/mica that the gold surface underwent sulfur modification during this treatment, which was believed to have only removed impurities from the gold surface. We also successfully developed a practical Pd material, SAPd, whose Pd was immobilized on sulfur-modified Au. With the lowest Pd-releasing levels and high recyclability, this is one of the best Pd materials thus far developed. Because it leaches extremely low levels of Pd into reaction mixtures, removal of the residual Pd is unnecessary using SAPd, even in syntheses involving pharmaceutical ingredients.
- Hoshiya, Naoyuki,Shimoda, Masahiko,Yoshikawa, Hideki,Yamashita, Yoshiyuki,Shuto, Satoshi,Arisawa, Mitsuhiro
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- Chitosan-supported palladium(0) catalyst for microwave-prompted Suzuki cross-coupling reaction in water
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A chitosan-supported palladium (Pd) (0) catalyst was prepared by simple adsorption of palladium(II) ion onto chitosan beads and a subsequent reduction process. To maintain mechanical stability, the chitosan-supported palladium(0) catalyst was cross-linked with either glutaraldehyde or diglycidyl ether polyethylene glycol. The catalysts were utilized for the Suzuki cross-coupling reaction in water. The catalyst, in the presence of a tetrabutylammonium bromide (TBAB) additive, showed excellent catalytic activity in microwave-prompted Suzuki cross-coupling reactions using various aryl halides and boronic acids. In addition, the catalyst was successfully reused up to five times without significant loss of catalytic activity.
- Yi, Song-Se,Lee, Dong-Ho,Sin, Eunyoung,Lee, Yoon-Sik
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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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- One-step synthesis of magnetically recyclable palladium loaded magnesium ferrite nanoparticles: application in synthesis of anticancer drug PCI-32765
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Novel Palladium nanoparticles supported nano Magnesium ferrite catalyst (Pd/MgFe2O4) was synthesized by one-step ultrasound assisted coprecipitation. In-situ formed by-products assisted salt cage calcination approach was employed to
- Dasari, Gopala Krishna,Sunkara, Satyaveni,Gadupudi, Purna Chandra Rao
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- Homogeneous and heterogeneous catalysts of organopalladium functionalized-polyhedral oligomeric silsesquioxanes for Suzuki-Miyaura reaction
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The mononuclear T8-Pd and multinuclear T10-Pd catalysts (3 and 6) were prepared from a reaction between Pd(COD)Cl2 (COD = 1,5-cyclooctadiene) and the corresponding octameric T8 and decameric T10 silsesquioxane cages, functionalized with pyridine-triazole ligands. The T8-Pd complex 3 featuring one Pd(II) center was employed as a homogeneous catalyst for Suzuki-Miyaura cross coupling in a 1:1 EtOH:H2O solvent. On the other hand, the multinuclear T10-Pd catalyst 6 (ca. 4.6 Pd for each T10 cage) was obtained as amorphous insoluble materials with exceptionally high molecular Pd loading (1.61 mmol Pd g-1). Under the same catalytic conditions, the homogeneous catalysts 3 exhibited slightly higher activity than the heterogeneous catalyst 6 (initial TOFs = 870 and 690 h-1, respectively). Furthermore, for 6, 4-(MeO)C6H4Br and PhB(OH)2 substrates were catalyzed in the presence of a low catalyst loading of 3.6 × 10-3 mol% Pd under aerobic conditions to afford the coupled product in 91% yield (i.e., turnover number (TON) = 2.5 × 104). The silsesquioxane-supported Pd catalyst 6 was recovered by simple centrifugation and reused for at least five catalytic cycles without a loss in activities.
- Ervithayasuporn, Vuthichai,Kwanplod, Kwanchanok,Boonmak, Jaursup,Youngme, Sujittra,Sangtrirutnugul, Preeyanuch
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- Highly efficient palladium(II) hydrazone based catalysts for the Suzuki coupling reaction in aqueous medium
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Synthesis of a new family of air stable palladium(ii)benzhydrazone complexes of the general formula [PdCl(PPh3)(L)] (where HL = thiophene aldehyde benzhydrazones) incorporating PPh3 and chloride as co-ligands has been described through a single and convenient step with good yields. All the new complexes have been fully characterized by means of elemental analysis, IR, UV-vis, and NMR spectral methods. The molecular structures of three of the complexes were determined by single crystal X-ray crystallography, which confirm the coordination mode of benzhydrazone and reveal the presence of a distorted square planar geometry around the Pd ion. The complexes 1-5 (0.05 mol%) have been found to be a highly active catalytic system in the mono and double Suzuki-Miyaura cross coupling reaction of deactivated aryl and heteroaryl bromides with different types of aryl boronic acids in neat water and the maximum yield was up to >99%. Notably, these catalysts work well with ultra-low loading of the catalysts and show high turnover numbers in a short time towards different substrates. Moreover, the catalysts could be simply recovered and reused five times without significant loss of efficiency.
- Muthumari, Subramanian,Ramesh, Rengan
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- 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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- 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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- PEG Click-Triazole Palladacycle: An Efficient Precatalyst for Palladium-Catalyzed Suzuki-Miyaura and Copper-free Sonogashira Reactions in Neat Water
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A novel water-soluble, phosphine-free PEG click triazole palladacycle has been successfully synthesized. As a precatalyst, the palladacycle exhibited superior catalytic activity towards Suzuki-Miyaura and copper-free Sonogashira cross-coupling in neat water with the turnover numbers (TONs) of up to 9.8×105. In addition, the catalyst could be reused at least 3 times without significant loss of reactivity. A water-soluble PEG click triazole palladacycle has been successfully synthesized. The palladacycle exhibited superior catalytic activity towards Suzuki-Miyaura and copper-free Sonogashira cross-coupling in neat water.
- Zhang, Guofu,Zhang, Wei,Luan, Yuxin,Han, Xingwang,Ding, Chengrong
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- Phosphine-free palladium acetate catalyzed Suzuki reaction in water
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Pd(OAc)2 in a mixture of water and poly(ethylene glycol) (PEG) is shown to be an extremely active catalyst for the Suzuki reaction of aryl iodides and bromides. The reaction can be conducted under mild conditions (50 °C) without the use of a microwave or phosphine ligand in high yields. The isolation of the products is readily performed by the extraction of diethyl ether, and the Pd(OAc)2-PEG can be reused without significant loss in activity.
- Liu, Leifang,Zhang, Yuhong,Wang, Yanguang
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- Palladium-catalyzed cross-coupling reaction of aryltriethoxysilanes with aryl bromides under basic aqueous conditions
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Aryltriethoxysilanes were cross-coupled with aryl bromides in high yield in the presence of a palladium catalyst and aqueous sodium hydroxide.
- Murata,Shimazaki,Watanabe,Masuda
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- Controlled synthesis of three dimensional mesoporous C3N4 with ordered porous structure for room temperature Suzuki coupling reaction
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We report on the synthesis of mesoporous graphitic C3N4 (MGCN-6) with 3D porous structure and Ia3d symmetry and controllable surface properties through a simple polymerization of an environmentally benign and non-toxic guanidine hydrochloride as a C and N precursor using KIT-6 with variable pore sizes as templates for Suzuki coupling reaction. The pore diameters (3.1–4.2 nm), specific surface areas (207–303 m2 g?1), and the specific pore volumes (0.58–0.71 cm3 g?1) of the MGCN-6 materials are finely controlled by varying the pore size of the templates used. The nano cavities of MGCN-6 with the highest specific surface area and a free amine groups are effectively utilized to chelate with Pd(OAC)2 and applied the prepared catalysts for Suzuki coupling reaction between aryl halides with phenylboronic acid derivatives under very mild and sustainable reaction conditions. The Pd(OAC)2/MGCN-6 is found to be very active and stable and exhibits an excellent reactivity and selectivity for all of substrates regardless of aryl halides with electron-withdrawing and electron donating groups at room temperature. The activity of the Pd(OAC)2/MGCN-6 is much higher than that of non-porous bulk graphitic carbon nitride and 2D mesoporous carbon nitride.
- Naidu Talapaneni, Siddulu,Ramadass, Kavitha,Benzigar, Mercy R.,Lakhi, Kripal S.,Yang, Jae-Hun,Ravon, Ugo,Albahily, Khalid,Vinu, Ajayan
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- Palladium catalysed cross-coupling of aryl bromides with functionalised arylboronic acids in the presence of a tetraphosphine ligand
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Cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane/[PdCl(C 3H5)]2 system catalyses efficiently the cross-coupling of aryl bromides with functionalised arylboronic acids. The electronic properties of the aryl
- Feuerstein, Marie,Berthiol, Florian,Doucet, Henri,Santelli, Maurice
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- LiCl-Accelerated multimetallic cross-coupling of aryl chlorides with aryl triflates
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While the synthesis of biaryls has advanced rapidly in the past decades, cross-Ullman couplings of aryl chlorides, the most abundant aryl electrophiles, have remained elusive. Reported here is the first general cross-Ullman coupling of aryl chlorides with aryl triflates. The selectivity challenge associated with coupling an inert electrophile with a reactive one is overcome using a multimetallic strategy with the appropriate choice of additive. Studies demonstrate that LiCl is essential for effective cross-coupling by accelerating the reduction of Ni(II) to Ni(0) and counteracting autoinhibition of reduction at Zn(0) by Zn(II) salts. The modified conditions tolerate a variety of functional groups on either coupling partner (42 examples), and examples include a three-step synthesis of flurbiprofen.
- Huang, Liangbin,Ackerman, Laura K. G.,Kang, Kai,Parsons, Astrid M.,Weix, Daniel J.
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- Applications of mesoporous titanium phosphonate functionalized with carboxylic groups
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Mesoporous titanium phosphonate functionalized with -COOH was synthesized by a simple co-condensation process with the use of 2-phosphonoacetic acid and titanium tetrachloride under acid conditions. The obtained mesoporous materials show high surface area and large pore volume, which were supported by XRD, TEM, SEM and N2 adsorption analysis. The integrity of the organophosphonate groups were further characterized by FTIR and NMR. Palladium nanoparticles were successfully supported onto the materials combined with a metal adsorption-reduction procedure, showing high activity for the Suzuki reaction. Furthermore, the obtained catalyst can be recovered and reused without significant decrease in catalytic activity. This journal is
- Li, Dongdong,Zhang, Yuping
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- Suzuki–Miyaura cross-coupling reaction assisted by palladium nanoparticles-decorated zeolite 13X nanocomposite: a greener approach
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Heterogeneous catalysts govern the field of catalysis due to their easy separation from a reaction mixture, reusability, and prevention of agglomeration, making them more efficient catalysts than homogeneous catalysts. Herein, we report the eco-friendly synthesis of a novel heterogeneous catalyst, viz. palladium nanoparticles (Pd NPs) decorated over zeolite 13X nanocomposite using dried fruits of Terminalia chebula Retz. as the reducing and stabilizing agent and its performance as a promising catalyst for the Suzuki–Miyaura coupling reactions. The particle size, crystallinity, morphology, and textural properties of the catalyst were identified using Fourier transform-infrared spectroscopy (FTIR), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HR-TEM), thermal gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and Brunauer–Emmett–Teller (BET) analysis which confirmed the presence of palladium nanoparticles on the surface of zeolite 13X. The FESEM images revealed the presence of spherical-shaped Pd NPs over the cubical particles of zeolite 13X. The average particle size of the palladium nanoparticles was found to be in the range of 6–7?nm and was polycrystalline in nature. From BET analysis, it was inferred that the decoration of Pd NPs decreased the surface area of zeolite 13X (615.5 m2/g to 548.334 m2/g), thus leaving pores unoccupied. This study showed the efficiency of this novel catalyst in the formation of biaryl derivatives using low palladium loadings (0.0012?mol%) giving good to excellent yields (90–99%) within short reaction times (10–225?min) with high TONs (> 79,000) and TOFs (> 21,000). Both electron-donating and electron-withdrawing aryl halides and aryl boronic acids reacted smoothly in the presence of K2CO3 as a base and EtOH/H2O (1:1) as the solvent. Besides, the catalyst could be recycled and reused for 5 consecutive runs with minimal loss of its efficiency. The supremacy of this catalyst could well be exploited in future for various organic transformations. Graphical abstract: [Figure not available: see fulltext.].
- Deepika, Raja,Sethuraman, Mathur Gopalakrishnan
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p. 1111 - 1128
(2022/01/22)
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- Visible Light Induced Aerobic Coupling of Arylboronic Acids Promoted by Hydrazone
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A visible-light-induced oxidative coupling of arylboronic acids has been developed for the synthesis of biaryls. The reaction that employs polydentate hydrazones as the bifunctional catalyst works smoothly under room temperature. It is compatible with a w
- Xia, Hongyu,Wang, Ganghu,Zhao, Dongbo,Zhu, Chunyin
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p. 922 - 929
(2022/02/10)
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- Synthesis of ultrafine AuPd bimetallic nanoparticles using a magnetite-cored poly(propyleneimine) dendrimer template and its sustainable catalysis of the Suzuki coupling reaction
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The poly(propyleneimine) PPI dendrimer with active amino groups and specific voids is an excellent template for the encapsulation and stabilization of size and shape-controlled metal nanoparticles. The magnetite-cored PPI dendrimer up to third generation was synthesized by a divergent method in our previous report. Bimetallic nanoparticles are more advantageous than monometallic nanoparticles in catalysis due to their synergistic effect between two metals, especially Au and Pd nanoparticles. Herein, we present the synthesis of highly monodispersed ultrafine AuPd bimetallic nanoparticles of size 3-6 nm using the magnetic-cored PPI dendrimer through a facile and convenient method without external stabilizers. The formation of the monodispersed bimetallic nanoparticles on the dendritic entity was confirmed through HRTEM, HRSEM, EDAX, XRD, XPS and VSM. The excellent structural behavior of the magnetic-cored PPI dendrimers proves their ability to encapsulate AuPd bimetallic nanoparticles, and also attain better dispersibility, stability, and improved efficacy compared to conventional dendrimer-encapsulated metal nanoparticles. Most predominantly, it was isolated by simple magnetic attraction. TheAuPd@PPI@Fe3O4/SiO2nanomaterial was utilized as a potential green catalyst in the Suzuki coupling reaction under ambient reaction conditions with greater reactivity and stability. Coupling products were characterized by1H and13C NMR. This material retained its catalytic activity in the coupling reaction for up to eight consecutive catalytic cycles.
- Rangasamy, Rajmohan,Lakshmi, Kannappan,Selvaraj, Mari
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p. 14227 - 14235
(2021/08/16)
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- Valorisation of urban waste to access low-cost heterogeneous palladium catalysts for cross-coupling reactions in biomass-derived γ-valerolactone
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Herein we report a simple protocol for the valorisation of a common urban biowaste. The lignocellulosic biomass obtained after the pre-treatment of pine needle urban waste is efficiently transformed into a low-cost support (PiNe) for the immobilization of Pd nanoparticles. The final Pd/PiNe heterogeneous catalyst features a small particle size (4.5 nm) and a metal loading (9.9 wt%) comparable with most commercially available and generally used counterparts. In this contribution, we tested the catalytic efficiency of the Pd/PiNe system in two representative cross-couplings, Heck and Hiyama reactions, and compared the results obtained with commercial Pd/C catalyst. The good reactivity in the biomass-derived solvent (GVL) confirms that the Pd/PiNe heterogeneous catalyst is a valid system that can be integrated into a waste valorization chain within a circular economy approach. In addition, the efficiency of the catalyst has also been extended to perform the challenging consecutive Hiyama-Heck reaction to afford differently substituted (E)-1,2-diarylethenes.
- Valentini, Federica,Ferlin, Francesco,Lilli, Simone,Marrocchi, Assunta,Ping, Liu,Gu, Yanlong,Vaccaro, Luigi
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supporting information
p. 5887 - 5895
(2021/08/23)
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- HFIP-Promoted Substitution in the Ferrocene Series: Smooth Approach towards Original Catalysts**
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Pseudo-benzylic substitution is an important reaction in the ferrocene series, especially to obtain ligands for catalysis. Herein, we described new reactions conditions, using fluorinated alcohols as both solvent and promoter, able to deliver iodoferrocen
- Erb, William,Carré, Victor,Roisnel, Thierry
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p. 5702 - 5716
(2021/09/03)
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- Complexes LNi(Cp)X with alkylamino-substituted N-heterocyclic carbene ligands (L) and their catalytic activity in the Suzuki—Miyaura reaction
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New nickel(ii) complexes of the general formula LNi(Cp)X (L is an N-heterocyclic carbene (NHC) ligand of the 1,2,4-triazole or imidazole series; Cp is the cyclopentadienyl anion; X = Cl, I) are reported. In these complexes, the NHC ligands (L) contain an alkylamino group at the 3 or 4 position of the heterocycle. The synthesized complexes and structurally similar complexes without an alkylamino group were tested for catalytic activity in the Suzuki—Miyaura reaction. The introduction of an alkylamino group into the NHC ligand leads to the enhancement of the catalytic activity of complexes with N,N′-diaryl-substituted NHC ligands of the imidazole series and a decrease in the activity of the complexes with N,N′-dialkyl-substituted NHC ligands of the 1,2,4-triazole series.
- Chernyshev, V. M.,Chesnokov, V. V.,Shevchenko, M. A.,Soliev, S. B.,Tafeenko, V. A.
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p. 1281 - 1289
(2021/08/10)
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- Integrated Suzuki Cross-Coupling/Reduction Cascade Reaction of meta-/para-Chloroacetophenones and Arylboronic Acids under Batch and Continuous Flow Conditions
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Overcoming the incompatibility of a pair of conflicting catalysts via a flow methodology has great significance in the practical applications for multistep organic transformations. In this study, a multiple continuous-flow system is developed, which can boost the reactivity and selectivity in a sequential enantioselective cascade reaction. During this process, a periodic mesoporous organosilica-supported Pd/carbene species as a Suzuki cross-coupling catalyst is packed in the first column reactor, whereas another periodic mesoporous organosilica-supported Ru/diamine species as an asymmetric transfer hydrogenation catalyst is packed in the second column reactor. As we envisioned, the initially Pd-catalyzed cross-coupling reaction of meta-/para-chloroacetophenones and aryl boronic acids followed by the subsequentially Ru-catalyzed reduction provides chiral biarylols with enhanced yields and enantioselectivities. Furthermore, the advantages of the easy handling and the simple procedure make this system an attractive application in a scale-up preparation of optically pure organic molecules under environmentally-friendly conditions.
- Li, Yilong,Wang, Chengyi,Chen, Qipeng,Li, Hongyu,Su, Yu,Cheng, Tanyu,Liu, Guohua,Tan, Chunxia
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p. 2338 - 2345
(2021/07/16)
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- Bathocuproine-Enabled Nickel-Catalyzed Selective Ullmann Cross-Coupling of Two sp 2-Hybridized Organohalides
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Cross-coupling reactions are essential for the synthesis of complex organic molecules. Here, we report a nickel-catalyzed Ullmann cross-coupling of two sp 2-hybridized organohalides, featuring high cross-selectivity when the two coupling partners are used in a 1:1 ratio. The high chemoselectivity is governed by the bathocuproine ligand. Moreover, the mild reductive reaction conditions allow that a wide range of functional groups are compatible in this Ullmann cross-coupling.
- Li, Yuqiang,Yin, Guoyin
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supporting information
p. 1657 - 1661
(2021/09/13)
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- Magnetic chitosan-functionalized cobalt-NHC: Synthesis, characterization and catalytic activity toward Suzuki and Sonogashira cross-coupling reactions of aryl chlorides
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Aryl chlorides are one of the most stable and available electrophiles, however, their coupling with nucleophiles remains a challenge in organic synthesis. Herein, we prepared a Cobalt-NHC (N-Heterocyclic carbene) complex anchored on magnetic chitosan nanoparticles and assayed its catalytic activity for the reactions of substituted phenylboronic acid and also phenlacetylene with derivatives of aryl chlorides. These reactions are of great importance since they are employed for the synthesis of unsymmetrical diarylethynes and biphenyls, which belong to a prime class of building blocks. The synthesized nanocatalyst was found to be highly efficient in Suzuki and Sonogashira coupling in terms of their activity and recyclability in polyethylene glycol (PEG) as a green reaction media under conditions of temperatures (70 and 100 °C) and Co loading (3 and 6 mol%). To the best of our knowledge, this is the first attempt of using cobalt-NHC complex for catalyzing the abovementioned reactions. Moreover, replacing the earth-abundant Cobalt-based catalyst as an alternative to high cost palladium make this approach promising from sustainable chemistry view.
- Hajipour, Abdol R.,Malek, Shaghayegh Sadeghi
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- Ligand-free Suzuki coupling reaction with highly recyclable ionic palladium catalyst, Ti1-xPdxO2-x (x?=?0.03)
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We synthesized a recyclable palladium ionic catalyst, Ti0.97Pd0.03O1.97, using a solution combustion method (SCM), and characterized by XRD and Rietveld refinement. The synthesized Pd ionic catalyst is stable, insensitive to moisture and air, and easy to handle. The new catalyst has exhibited a phenomenal result for the Suzuki-Miyaura cross-coupling reaction with a broad substrate scope, and the reaction proceeds in an aqueous medium. The new catalyst proved beneficial and produced excellent yields irrespective of aryl halide used in the reaction (electron-rich or electron-poor or heterocyclic compounds) and shown a turnover frequency (TOF) of 14–25 h?1 for different reactions. The catalyst was coated on a cordierite monolith (Mg2Al4Si5O18), which enhanced the applicability of the catalyst, and made the handling and recycling of the catalyst very easy. Suzuki Miyaura reaction was carried out using both Pd-powder catalysts as well as the Pd-coated honeycomb, which gave almost similar results. We have demonstrated the recyclability of Pd coated cordierite monolith and shown the superiority of the catalyst over the other Pd catalysts for the Suzuki-Miyaura reaction.
- Bhat K, Shrikanth,Lanke, Veeranjaneyulu,Prasad, Jagadeesh Dasappa,Prabhu, Kandikere Ramaiah
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- Self-Assembled Multilayer Iron(0) Nanoparticle Catalyst for Ligand-Free Carbon-Carbon/Carbon-Nitrogen Bond-Forming Reactions
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Self-assembled multilayer iron(0) nanoparticles (NPs, 6-10 nm), namely, sulfur-modified Au-supported Fe(0) [SAFe(0)], were developed for ligand-free one-pot carbon-carbon/carbon-nitrogen bond-forming reactions. SAFe(0) was successfully prepared using a well-established metal-nanoparticle catalyst preparative protocol by simultaneous in situ metal NP and nanospace organization (PSSO) with 1,4-bis(trimethylsilyl)-1,4-dihydropyrazine (Si-DHP) as a strong reducing agent. SAFe(0) was easy to handle in air and could be recycled with a low iron-leaching rate in reaction cycles.
- Akiyama, Toshiki,Arisawa, Mitsuhiro,Haneoka, Hitoshi,Harada, Kazuo,Hasegawa, Jun-Ya,Honma, Tetsuo,Mashima, Kazushi,Sato, Yoshihiro,Shimoda, Shuhei,Shio, Yasunori,Suzuki, Takeyuki,Tamenori, Yusuke,Tsurugi, Hayato,Tsuruta, Kazuki,Wada, Yuki,Yamada, Makito
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supporting information
p. 7244 - 7249
(2020/10/12)
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- Design, Synthesis, Characterization and Application of BNPs@SiO2(CH2)3NH-CC-AMP-Pd (0) as a New Reusable Nano-Catalyst for Suzuki and Heck Cross-Coupling Reactions
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Abstract: A simple and effective method was used for the successful preparation of the Boehmite@(CH2)3NH-CC-AMP-Pd (0) NPs as an environmentally friendly heterogeneous nano-catalyst. The synthesized nano-catalyst was well identified by different techniques like FT-IR, XRD, XPS, TEM, SEM, EDX, TGA, mapping, and ICP analysis. The BNPs@SiO2(CH2)3NH-CC-AMP-Pd was used as a recoverable nano-catalyst for Suzuki‐Miyaura and Mizoroki‐Heck coupling reactions under mild, green and sustainable conditions with excellent yields (H2O, EtOH as solvent for Suzuki reaction and solvent-free conditions for Heck reaction). Also, the distribution of palladium on the catalyst surface is uniform and the average palladium size is between 20 and 30?nm. Compared to similar works, this protocol has some of the important aspects such as: thermal and mechanical stability of the catalyst, low palladium leaching (9.7%), the simplicity of the preparation, the availability of raw materials, not expensive, no need for neutral atmosphere, appropriate times, green conditions, use low amount of catalyst (1.42?mol%) and reused catalyst for several consecutive times (at least seven times). Graphic Abstract: [Figure not available: see fulltext.]
- Khodamorady, Minoo,Bahrami, Kiumars
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p. 1571 - 1590
(2019/12/11)
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- Visible light-driven Suzuki-Miyaura reaction by self-supported Pd nanocatalysts in the formation of Stille coupling-based photoactive microporous organic polymers
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Stille coupling was applied to synthesize microporous organic polymers (MOPs). Metallic Pd was in situ self-supported during the networking of 1,3,6,8-tetrabromopyrene with 1,4-bis(tributylstannyl)benzene to form Stille coupling-based MOP (St-MOP)?Pd. The size of St-MOP particles and the amount of metallic Pd in St-MOP?Pd depended on the amount of Pd catalyst. As the amount of Pd catalyst increased, the size of St-MOP particles decreased with an increase of metallic Pd, due to the increased St-MOP nuclei in the early growth stage of St-MOP. The St-MOP bearing pyrenes showed absorption and emission of visible light and St-MOP?Pd showed excellent catalytic performance in the visible light-driven Suzuki-Miyaura coupling. The optimal St-MOP?Pd-2 (0.14 mol% Pd) showed a TON of 657 and a TOF of 219 h-1 in the visible light-driven Suzuki-Miyaura coupling of 1-acetyl-4-bromobenzene and phenylboronic acid at 25 °C. The optimal amount of St-MOP and metallic Pd in St-MOP?Pd was critical to achieve excellent catalytic performance. The overall photocatalytic principles of St-MOP?Pd were rationalized by computational simulation. This journal is
- Ahn, Tae Kyu,Choi, Sung Jae,Jo, Bonghyun,Kim, Hae Jin,Ko, Kyoung Chul,Ko, Yoon-Joo,Lee, Sang Moon,Ryu, Sang Hyun,Seon, Ji Hui,Son, Seung Uk
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p. 5535 - 5543
(2020/09/17)
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- Aqueous Suzuki-Miyaura coupling with ultralow palladium loading and simple product separation
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The diphosphine ligand N, N -bis(diphenylphosphanylmethyl)-aniline (bdppma) and PdCl 2afforded a Suzuki-Miyaura catalyst [(bdppm-)PdCl 2] that was highly efficient at an ultralow catalyst loading (0.001 mol%) in 20:1 H 2O-EtOH. This low catalyst loading in an aqueous solvent system permitted simple product separation by direct filtration without the need for chromatography. The ligand bdppma imparted surprisingly better reactivity than that achieved with other bidentate diphosphine ligands, but the catalytic system had a slightly narrower substrate scope than some similar Pd catalysts reported previously.
- Yang, Wei,Xu, Wen-Di,Ning, Jin-Jiao,Ren, Zhi-Gang,Young, David James
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supporting information
p. 1303 - 1307
(2020/08/21)
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- Air- And moisture-stable Xantphos-ligated palladium dialkyl complex as a precatalyst for cross-coupling reactions
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Although xantphos has been employed in a variety of palladium-catalyzed cross-coupling reactions, there has been little progress in developing Xantphos-ligated precatalysts. In this report, we describe a Xantphos-ligated palladium dialkyl complex that acts as a powerful precatalyst for C-N, C-S, and C-C cross-coupling reactions. This precatalyst is air- and moisture stable but can be thermally activated in the absence of external reagents. Additionally, potential catalyst inhibitors are not generated during the precatalyst activation. This complex thus represents a convenient alternative to previously reported classes of Xantphos-ligated precatalysts.
- Takahashi, Rina,Kubota, Koji,Ito, Hajime
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supporting information
p. 407 - 410
(2020/01/13)
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- A Convoluted Polyvinylpyridine-Palladium Catalyst for Suzuki-Miyaura Coupling and C?H Arylation
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The development of highly active and reusable supported catalysts for Suzuki-Miyaura coupling and catalytic C?H arylation is important for fundamental and applied chemistry, with these reactions being used to produce medical compounds and functional materials. Herein, we found that a mesoporous composite made of a linear poly(4-vinylpyridine) and tetrachloropalladate acted as a dual-mode catalyst for a variety of cross-coupling reactions, with both Pd nanoparticles and a Pd complex catalyst being observed under different conditions. The polyvinylpyridine-palladium composite 1 was readily prepared via the molecular convolution of poly(4-vinylpyridine) and sodium tetrachloropalladate to provide a hardly soluble polymer-metal composite. The Suzuki-Miyaura coupling and the C?H arylation of aryl chlorides and bromides with arylboronic acids, thiophenes, furans, benzene, and anisole proceeded in the presence of 0.004 mol% (40 mol ppm) to 1 mol% Pd of 1 to afford the corresponding coupling products in high yields. Furthermore, the catalyst was reused without an appreciable loss of activity. Pharmaceutical compounds and functional materials were synthesized via the coupling reactions. N2 gas adsorption/desorption analysis indicated that the catalyst had a mesoporous nature, which played a crucial role in the catalysis. In the Suzuki-Miyaura couplings, in situ generated palladium nanoparticles in the polymer matrix were catalytically active, while a polymeric Pd(II) complex was crucial in the C?H arylations. These catalytic species were investigated via XAFS, XPS, far-infrared absorption, and Raman spectroscopies, as well as DFT calculations. (Figure presented.).
- Ohno, Aya,Sato, Takuma,Mase, Toshiaki,Uozumi, Yasuhiro,Yamada, Yoichi M. A.
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supporting information
p. 4687 - 4698
(2020/09/07)
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- Synthesis and Characterization of RhIII-MII(M = Pt, Pd) Heterobimetallic Complexes Based on a Bisphosphine Ligand: Tandem Reactions Using Ethanol
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1,1-Bis(diphenylphosphino)methane (dppm) was used as a linker ligand for the preparation of a series of heterobimetallic RhIII-PtII and RhIII-PdII complexes. These complexes were characterized by means of several analytical and spectroscopic methods. The catalytic activities of these heterobimetallic complexes were carried out in three different tandem reactions: Namely, transfer hydrogenation (TH)/dehalogenation (DH), TH/Suzuki-Miyaura coupling, and coupling of benzylic alcohols with nitrobenzenes for Schiff base construction. Ethanol was used as both the solvent and an inexpensive TH reagent, where a broad substrate scope was demonstrated for these tandem reactions. All reactions proceeded smoothly in air at 80-90 °C. The RhIII-PdII complex showed superior catalytic performance in comparison to the RhIII-PtII complexes, its monometallic counterparts, and mixtures of monometallic (RhIII + PdII) complexes. The result demonstrates a cooperative effect between the Rh and Pd metal centers. A mechanism for the catalytic tandem reactions was investigated. It was found that alcohol medium and base are essential.
- Mandegani, Zeinab,Nahaei, Asma,Nikravesh, Mahshid,Nabavizadeh, S. Masoud,Shahsavari, Hamid R.,Abu-Omar, Mahdi M.
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p. 3879 - 3891
(2020/11/13)
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- Decarbonylative Suzuki-Miyaura Cross-Coupling of Aroyl Chlorides
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Herein, we report a catalyst system for Pd-catalyzed decarbonylative Suzuki-Miyaura cross-coupling of aroyl chlorides with boronic acids to furnish biaryls. This strategy is suitable for a broad range of common aroyl chlorides and boronic acids. The synthetic utility is highlighted in the direct late-stage functionalization of pharmaceuticals and natural products capitalizing on the presence of carboxylic acid moiety. Extensive mechanistic and DFT studies provide key insight into the reaction mechanism and high decarbonylative cross-coupling selectivity.
- Zhou, Tongliang,Xie, Pei-Pei,Ji, Chong-Lei,Hong, Xin,Szostak, Michal
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supporting information
p. 6434 - 6440
(2020/09/02)
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- Decarboxylative Suzuki-Miyaura coupling of (hetero)aromatic carboxylic acids using iodine as the terminal oxidant
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A novel methodology for the decarboxylative Suzuki-Miyaura-type coupling has been established. This process uses iodine or a bromine source as both the decarboxylation mediator and the terminal oxidant, thus avoiding the need for stoichiometric amounts of transition metal salts previously required. Our new protocol allows for the construction of valuable biaryl architectures through the coupling of (hetero)aromatic carboxylic acids with arylboronic acids. The scope of this decarboxylative Suzuki reaction has been greatly diversified, allowing for previously inaccessible non-ortho-substituted aromatic acids to undergo this transformation. The procedure also benefits from low catalyst loadings and the absence of stoichiometric transition metal additives.
- Quibell, Jacob M.,Duan, Guojian,Perry, Gregory J.P.,Larrosa, Igor
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supporting information
p. 6445 - 6448
(2019/06/07)
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- Sustainable Ligand-Free, Palladium-Catalyzed Suzuki–Miyaura Reactions in Water: Insights into the Role of Base
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A simple and efficient system was developed for the ligand-free Pd-catalyzed Suzuki–Miyaura reaction in water under mild conditions. Quaternary ammonium hydroxides with long chains were found to be very suitable bases. This ligand-free Pd-catalyzed Suzuki–Miyaura reaction showed improved durability in water with Pd loadings decreased to ppm level. Bases were shown to stabilize active palladium species in addition to acting as a base during the catalytic process. In the catalytic system with a strong base, the soluble active PdII ion exhibited anti-reduction properties, which prevented aggregation and deactivation of Pd species. The entire catalytic system could be recycled after separating the product by simple filtration. The water-compatible and air-stable effective catalytic protocol described herein represents an attractive and green synthetic advance in Suzuki–Miyaura couplings.
- Wang, Yanyan,Liu, Yuanyuan,Zhang, Wei-qiang,Sun, Huaming,Zhang, Kan,Jian, Yajun,Gu, Quan,Zhang, Guofang,Li, Jiyang,Gao, Ziwei
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p. 5265 - 5273
(2019/11/29)
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- Cellulose supported Pd(II) complex catalyzed carbon-carbon bonds formation
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Corn-cobs are an agro-industrial waste and composed of cellulose mostly. In this study cellulose was isolated from the waste corn-cobs and modified to polymeric hydroxamic acid palladium complex 1 and characterized by using a variety of spectroscopic methods such as field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The complex 1 exhibited high catalytic activity towards Suzuki and Heck coupling reactions of activated and deactivated aryl halides to give the respective coupling products with high yield. Moreover, the complex 1 was recovered and recycled five times with no considerable loss of catalytic overall performance.
- Sarkar, Shaheen M.,Rashid,Karim, Kaykobad Md. Rezaul,Mustapha, Siti Noor Hidayah,Lian, Yuen Mei,Zamri, Normaiza,Khan, Md. Maksudur Rahman,O'Reilly, Emmet J.,Rahman, Md. Lutfor
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p. 2856 - 2861
(2019/01/03)
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- A group of diphosphine-thiosemicarbazone complexes of palladium: Efficient precursors for catalytic C–C and C–N coupling reactions
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Reaction of 4-R-benzaldehyde thiosemicarbazone (denoted in general as HL-R; where H stands for the dissociable acidic proton and R (R = OCH3, CH3, H, Cl and NO2) for the substituent) with [Pd(dppe)(EtOH)2]2+, generated in situ via interaction of [Pd(dppe)Cl2] (dppe = 1,2-bis(diphenylphosphino)ethane) with AgNO3 in hot ethanol, in the presence of triethylamine affords a group of orange complexes of the type [Pd(dppe)(L-R)]NO3. Structures of [Pd(dppe)Cl2] and [Pd(dppe)(L-OCH3)]NO3 have been determined by X-ray crystallography. In the [Pd(dppe)(L-R)]NO3 complexes, the thiosemicarbazone ligands are coordinated to the metal center as monoanionic bidentate N,S-donors forming five-membered chelate rings. The [Pd(dppe)(L-R)]NO3 complexes show intense absorptions in the visible and ultraviolet regions, which have been analyzed by TDDFT calculations. All the [Pd(dppe)(L-R)]NO3 complexes are found to efficiently catalyze Suzuki-type C–C and Buchwald-type C–N coupling reactions.
- Thapa, Kiran,Paul, Piyali,Bhattacharya, Samaresh
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p. 232 - 239
(2018/11/06)
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- Palladium on magnetic Irish moss: A new nano-biocatalyst for suzuki type cross-coupling reactions
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A novel heterogeneous magnetic palladium nano-biocatalyst was designed by utilizing Irish moss, a family of sulfated polysaccharides extracted from algae, as a natural biopolymer. This magnetic Irish moss decorated with palladium (Pd–Fe3O4@IM) to form a biomagnetic catalytic system was synthesized and well characterized by FT–IR analysis, X-ray powder diffraction, field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, atomic absorption spectroscopy and transmission electron microscopy. The catalyst was stable to air and moisture and displayed high catalytic activity in ligand-free Suzuki–Miyaura cross-coupling reactions conducted under green chemistry reaction conditions. The aromatic ketones are produced by the cross-coupling reaction between acid chlorides and aryl boronic acid derivatives in high yields.
- Dolatkhah, Zahra,Javanshir, Shahrzad,Bazgir, Ayoub,Hemmati, Behnaz
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- Isinglass–palladium as collagen peptide–metal complex: a highly efficient heterogeneous biocatalyst for Suzuki cross-coupling reaction in water
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The class of bio-nanocatalysts (BNCs) is an evolving innovation that synergistically assimilates advanced nanotechnology with biotechnology. BNCs promote green processes due to their low consumption of chemicals and the absence of toxic by-products. Isinglass (IG), from the Dutch huizenblaas (sturgeon bladder), containing approximately 98% protein collagen, is used to support the immobilization of palladium (Pd) nanoparticles. This process leads to Pd/IG composite, a new class of heterogeneous collagen peptides–metal BNCs that exhibit high catalytic activity and reusability for ligand-free Suzuki coupling reaction in water. Additionally, these BNCs are obviously active in the cross-coupling reaction between acid chloride and arylboronic acid, producing a high yield of the desired ketones. The synthesized BNCs are well-characterized by Fourier transform infrared spectroscopy, field emission scanning electron microscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, energy-dispersive X-ray spectroscopy, inductively coupled plasma, and transmission electron microscopy.
- Dolatkhah, Zahra,Javanshir, Shahrzad,Bazgir, Ayoob
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p. 1473 - 1481
(2019/06/11)
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- MgFe2O4@SiO2-PrNH2/Pd/bimenthonoxime core-shell magnetic nanoparticles as a recyclable green catalyst for heterogeneous Suzuki cross-coupling in aqueous ethanol
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Magnetically recoverable MgFe2O4@SiO2-PrNH2/Pd/bimenthonoxime nanoparticles were prepared and characterized by SEM, EDX, TEM, XRD, XPS, ICP, VSM and FT-IR. The nanocatalyst was used for Suzuki cross-coupling in
- Mahmoudzadeh, Mansour,Mehdipour, Ebrahim,Eisavi, Ronak
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p. 841 - 859
(2019/04/26)
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- Nanosized Bispyrazole-Based Cryptand-Stabilized Palladium(0) Nanoparticles: A Reusable Heterogeneous Catalyst for the Suzuki-Miyaura Coupling Reaction in Water
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A macrobicyclic cryptand with a long rigid cavity incorporating a chelating bispyrazole moiety in each of the three bridges was synthesized. The multiple chelating metal binding sites were utilized for the controlled synthesis and stabilization of ultrafine palladium nanoparticles (Pd NPs) of nearly ~2 nm size. The as-synthesized Pd NPs were characterized by X-ray photoelectron spectroscopy, transmission electron microscopy, and powder X-ray diffraction. The well-dispersed cryptand-stabilized nanoparticles are found to catalyze the C-C bond-forming Suzuki-Miyaura reaction heterogeneously using water as a green solvent.
- Verma, Ashish,Tomar, Kapil,Bharadwaj, Parimal K.
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supporting information
p. 1003 - 1006
(2019/01/26)
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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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- Solid-state Suzuki-Miyaura cross-coupling reactions: Olefin-accelerated C-C coupling using mechanochemistry
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The Suzuki-Miyaura cross-coupling reaction is one of the most reliable methods for the construction of carbon-carbon bonds in solution. However, examples for the corresponding solid-state cross-coupling reactions remain scarce. Herein, we report the first broadly applicable mechanochemical protocol for a solid-state palladium-catalyzed organoboron cross-coupling reaction using an olefin additive. Compared to previous studies, the newly developed protocol shows a substantially broadened substrate scope. Our mechanistic data suggest that olefin additives might act as dispersants for the palladium-based catalyst to suppress higher aggregation of the nanoparticles, and also as stabilizer for the active monomeric Pd(0) species, thus facilitating these challenging solid-state C-C bond forming cross-coupling reactions.
- Seo, Tamae,Ishiyama, Tatsuo,Kubota, Koji,Ito, Hajime
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p. 8202 - 8210
(2019/09/19)
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- Efficient construction of C–C bonds from aryl halides/aryl esters with arylboronic acids catalysed by palladium(II) thiourea complexes
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A new set of palladium(II) complexes comprising phenyl(thiazolyl)thiourea ligands have been successfully synthesized and characterized with the aid of analytical as well as spectral (IR, UV–visible and NMR) methods. A distorted square-planar geometry with N^S coordination mode of thiourea ligands in the new palladium complexes was corroborated by single-crystal X-ray diffraction methods. Interestingly, the palladium(II) thiourea complexes showed the highest catalytic activity with 0.1 mol% catalyst loading in Suzuki–Miyaura cross-coupling reactions utilizing a range of aryl bromides/unactivated aryl chlorides with arylboronic acids as coupling partners in aqueous–organic media. Syntheses of diaryl ketones using aryl esters and arylboronic acids as coupling partners were also achieved with low catalyst loading within 20 h. The potential of our catalyst was demonstrated by its wide substrate scope, low catalyst loadings and high isolated yield. Moreover, the influences of key parameters like solvent, base, temperature and catalyst loading were also investigated.
- Thimma Sambamoorthy, Manikandan,Rengan, Ramesh,Jan Grzegorz, Malecki
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- A highly efficient and recyclable NiCl2(dppp)/PEG-400 system for Suzuki-Miyaura reaction of aryl chlorides with arylboronic acids
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NiCl2(dppp) in PEG-400 is shown to be a highly efficient catalyst for Suzuki-Miyaura coupling of aryl chlorides with arylboronic acids. The reaction could be conducted at 100 °C using K3PO4 as base, yielding a variety of biaryls in good to excellent yields. The isolation of the products was readily performed by extraction with petroleum ether and NiCl2(dppp)/PEG-400 system could be easily recycled and reused up to five times without significant loss of activity. Our system not only avoids the use of easily volatile and toxic dioxane or toluene as a solvent but also solves the basic problem of nickel catalyst reuse.
- Liao, Yang,Yang, Weisen,Wei, Ting,Cai, Mingzhong
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supporting information
p. 1134 - 1142
(2019/04/10)
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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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- Palladium-catalysed room-temperature Suzuki–Miyaura coupling in water extract of pomegranate ash, a bio-derived sustainable and renewable medium
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An agro waste-derived, ‘water extract of pomegranate ash’ (WEPA), has been utilized for the first time as a renewable medium for Pd(OAc)2-catalysed Suzuki–Miyaura cross-coupling at room temperature. This method offers a simple and sustainable synthesis of biaryls from aryl halides and arylboronic acids under ligand- and external base-free aerobic and ambient conditions. This method has been found effective for both activated and unactivated aryl halides in the production of biaryls with moderate to nearly quantitative yields. The protocol shows high chemoselectivity over identical/similar reactive sites in aryl halides (i.e. selectivity over identical halogens or different halogens of aryl halides). This method exhibits high regioselectivity, i.e. the selective reactivity of a halogen over other identical halogens at different positions on the aromatic nucleus. Therefore, we disclose here a clean, benign, substantial chemo- and regioselective and highly economic alternative method for the palladium-assisted synthesis of biaryls using an agro waste-derived medium.
- Appa, Rama Moorhy,Prasad, S. Siva,Lakshmidevi, Jangam,Naidu, Bandameeda Ramesh,Narasimhulu, Manchala,Venkateswarlu, Katta
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- A Polystyrene-Cross-Linking Tricyclohexylphosphine: Synthesis, Characterization and Applications to Pd-Catalyzed Cross-Coupling Reactions of Aryl Chlorides
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A polystyrene-cross-linking tricyclohexylphosphine (PS-TCP) was synthesized through radical emulsion polymerization of 4-tert-butylstyrene as a monomer and tris(trans-4-styrylcyclohexyl)phosphine as a threefold cross-linker. The PS-TCP showed enhanced ligand performance compared to the corresponding polystyrene-triphenylphosphine hybrid PS-TPP and tricyclohexylphosphine in Pd-catalyzed Suzuki–Miyaura and Buchwald–Hartwig reactions of aryl chlorides.
- Arashima, Junya,Iwai, Tomohiro,Sawamura, Masaya
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supporting information
p. 411 - 415
(2019/02/03)
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- A green synthesis of biaryls in water catalyzed by palladium nanoparticles immobilized on N-amidinoglycine-functionalized iron oxide nanoparticles
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Fe3O4 nanoparticles were prepared by co-precipitation and coated with SiO2 following the St?ber process. N-Amidinoglycine amino acid was then covalently connected to provide an excellent ligand for the immobilization of Pd nanoparticles. The resulting material was characterized by FE-SEM, TEM, EDX, XRD, VSM and ICP-AES analysis. The Fe3O4@SiO2@N-amidinoglycine@Pd0 proved to be a highly active catalyst for the Suzuki coupling reactions of various aryl halides with substituted phenylboronic acids in water, giving the desired products in excellent yields for short reaction times. Moreover, this catalyst can be easily recovered by using an external magnet and directly reused for several times without significant loss of activity.
- Rafiee, Fatemeh,Mehdizadeh, Nasrin
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p. 295 - 300
(2018/03/23)
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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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- 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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- 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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- Rapid “Mix-and-Stir” Preparation of Well-Defined Palladium on Carbon Catalysts for Efficient Practical Use
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A facile direct deposition approach for the preparation of recyclable Pd/C catalysts simply by stirring a solution of tris(dibenzylideneacetone)dipalladium(0) with a suitable carbon material was evaluated. An extraordinarily rapid catalyst preparation procedure (0 centers onto the highly accessible surface area and the avoidance of ill-defined PdII/Pd0 states.
- Yakukhnov, Sergey A.,Pentsak, Evgeniy O.,Galkin, Konstantin I.,Mironenko, Roman M.,Drozdov, Vladimir A.,Likholobov, Vladimir A.,Ananikov, Valentine P.
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p. 1869 - 1873
(2018/04/30)
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- Palladium N-Heterocyclic Carbene Complex of Vitamin B1 Supported on Silica-Coated Fe3O4 Nanoparticles: A Green and Efficient Catalyst for C–C Coupling
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Abstract: Fe3O4@SiO2 nanoparticles were prepared by hydrolysis of TEOS in the presence of Fe3O4 nanoparticles that were synthesized through co-precipitation procedure. Then, thiamine hydrochloride (VB1) was covalently connected with silica to provide a biodegradable, nontoxic and inexpensive NHC ligand for the formation of complex with palladium. This magnetic bionanocatalyst was characterized using FT-IR, XPS, FE-SEM, TEM, EDX, XRD, VSM, TGA and ICP-AES analysis. The Fe3O4@SiO2@VB1-Pd was found as a magnetically separable and highly active catalyst for the Suzuki coupling reactions of various aryl halides with substituted phenylboronic acids. Under appropriate conditions, all reactions afforded the desired products in excellent yields at short reaction times. Moreover, this catalyst can be easily recovered by using a magnetic field and directly reused for five times in this cross coupling with good yield and suitable time. Graphical Abstract: [Figure not available: see fulltext.]
- Rafiee, Fatemeh,Mehdizadeh, Nasrin
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p. 1345 - 1354
(2018/03/28)
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- Sublimable bis(β-iminoenolate)palladium(II) complexes and their application as catalysts in Suzuki-Miyaura reactions
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The Pd(II) complexes strongly chelated by two β-iminoenolate ligands were easily synthesized in only two steps, and purified based on their sublimable and highly stable property. The Pd(II) complexes anchored on a silica surface showed good catalytic activity in Suzuki-Miyaura reactions (up to 99% yield with 0.05 mol% catalyst). They tolerated a wide range of temperature (rt~110 °C) and various solvents, and could be reused multiple times after simple recovering process.
- Kim, Mi Jin,Jung, Myung Jin,Kim, Yeong Joon,Sung, Ha Kyoung,Lee, Ju Young,Ham, Sung Jin,Park, Chan Pil
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supporting information
p. 2989 - 2993
(2018/07/02)
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