- Microwave-accelerated Suzuki-Miyaura coupling reactions using potassium aryltrifluoroborates
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The microwave-accelerated Suzuki-Miyaura coupling of bromoarenes and potassium aryltrifluoroborates in good to excellent yields is described. The method does not require the use of phosphine ligands or phase-transfer catalysts and reactions are complete in 20 minutes. Georg Thieme Verlag Stuttgart.
- Harker, Rebecca L.,Crouch, R. David
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- Polysulfide Anions as Visible Light Photoredox Catalysts for Aryl Cross-Couplings
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Polysulfide anions are endowed with unique redox properties, attracting considerable attentions for their applications in alkali metals-sulfur batteries. However, the employment of these anionic species in redox catalysis for small molecule synthesis remains underdeveloped due to their moderate-poor electrochemical potential in the ground state, whereas some of them are characterized by photoabsorptions in visible spectral regions. Herein, we disclose the use of polysulfide anions as visible light photoredox catalysts for aryl cross-coupling reactions. The reaction design enables single-electron reduction of aryl halides upon the photoexcitation of tetrasulfide dianions (S42-). The resulting aryl radicals are engaged in (hetero)biaryl cross-coupling, borylation, and hydrogenation in a redox catalytic regime involving S4?-/S42- and S3?-/S32- redox couples.
- Li, Haoyu,Tang, Xinxin,Pang, Jia Hao,Wu, Xiangyang,Yeow, Edwin K. L.,Wu, Jie,Chiba, Shunsuke
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supporting information
p. 481 - 487
(2021/01/13)
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- A Highly Efficient Monophosphine Ligand for Parts per Million Levels Pd-Catalyzed Suzuki–Miyaura Coupling of (Hetero)Aryl Chlorides
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A new indolylphosphine WK-phos has been synthesized for Pd-catalyzed Suzuki–Miyaura coupling of (hetero)aryl chlorides with (alkyl)arylboronic acids. Comprising this newly developed ligand with palladium(II) acetate, the resulting catalyst system was found to be highly effective in facilitating the reaction even when the catalyst loading reaches parts per million levels (e.g. 10 ppm). These examples represent one of the lowest catalyst loadings reported to date of employing monophosphine (e.g. Ar-PCy2) for Suzuki–Miyaura reactions. The ligand geometry has also been well-characterized by single-crystal X-ray crystallography.
- Choy, Pui Ying,Yuen, On Ying,Leung, Man Pan,Chow, Wing Kin,Kwong, Fuk Yee
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p. 2846 - 2853
(2020/04/09)
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- Orthogonal Nanoparticle Catalysis with Organogermanes
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Although nanoparticles are widely used as catalysts, little is known about their potential ability to trigger privileged transformations as compared to homogeneous molecular or bulk heterogeneous catalysts. We herein demonstrate (and rationalize) that nanoparticles display orthogonal reactivity to molecular catalysts in the cross-coupling of aryl halides with aryl germanes. While the aryl germanes are unreactive in LnPd0/LnPdII catalysis and allow selective functionalization of established coupling partners in their presence, they display superior reactivity under Pd nanoparticle conditions, outcompeting established coupling partners (such as ArBPin and ArBMIDA) and allowing air-tolerant, base-free, and orthogonal access to valuable and challenging biaryl motifs. As opposed to the notoriously unstable polyfluoroaryl- and 2-pyridylboronic acids, the corresponding germanes are highly stable and readily coupled. Our mechanistic and computational studies provide unambiguous support of nanoparticle catalysis and suggest that owing to the electron richness of aryl germanes, they preferentially react by electrophilic aromatic substitution, and in turn are preferentially activated by the more electrophilic nanoparticles.
- Fricke, Christoph,Sherborne, Grant J.,Funes-Ardoiz, Ignacio,Senol, Erdem,Guven, Sinem,Schoenebeck, Franziska
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supporting information
p. 17788 - 17795
(2019/11/13)
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- Catalyst shuttling enabled by a thermoresponsive polymeric ligand: Facilitating efficient cross-couplings with continuously recyclable ppm levels of palladium
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A polymeric monophosphine ligand WePhos has been synthesized and complexed with palladium(ii) acetate [Pd(OAc)2] to generate a thermoresponsive pre-catalyst that can shuttle between water and organic phases, with the change being regulated by temperature. The structure of the polymeric ligand was confirmed with matrix-assisted laser desorption/ionization-time-of-flight (MALDI-TOF) mass spectrometry and size-exclusion chromatography (SEC) analysis, as well as nuclear magnetic resonance (NMR) measurements. This polymeric metal complex enables highly efficient Pd-catalyzed cross-couplings and tandem reactions using 50 to 500 ppm palladium, and this can facilitate reactions that are tolerant to a broad spectrum of (hetero)aryl substrates and functional groups, as demonstrated with 73 examples with up to 99% isolated yields. Notably, 97% Pd remained in the aqueous phase after 10 runs of catalyst recycling experiments, as determined via inductively coupled plasma-atomic emission spectrometry (ICP-AES) measurements, indicating highly efficient catalyst transfer. Furthermore, a continuous catalyst recycling approach has been successfully developed based on flow chemistry in combination with the catalyst shuttling behavior, allowing Suzuki-Miyaura couplings to be conducted at gram-scales with as little as 10 ppm Pd loading. Given the significance of transition-metal catalyzed cross-coupling and increasing interest in sustainable chemistry, this work is an important step towards the development of a responsive catalyst, in addition to having high activity, by tuning the structures of the ligands using polymer science.
- Wang, Erfei,Chen, Mao
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p. 8331 - 8337
(2019/09/30)
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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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- Insights into the Catalytic Activity of [Pd(NHC)(cin)Cl] (NHC=IPr, IPrCl, IPrBr) Complexes in the Suzuki–Miyaura Reaction
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The influence of C4,5-halogenation on palladium N-heterocyclic carbene complexes and their activity in the Suzuki–Miyaura reaction were investigated. Two [Pd(NHC)(cin)Cl] complexes bearing IPrCl and IPrBr ligands (IPr=1,3-bis(2,6-diisopropyl-phenyl)imidazol-2-ylidene; cin=cinnamyl) were synthesized. After determining the electronic and steric properties of these ligands, their properties were compared to those of [Pd(IPr) (cin)Cl]. The three palladium complexes were studied by using DFT calculations to delineate their behavior in the activation step leading to the putative 12-electron active catalyst. Experimentally, their catalytic activity in the Suzuki–Miyaura reaction involving a wide range of coupling partners (30 entries) at low catalyst loading was studied.
- Izquierdo, Frédéric,Zinser, Caroline,Minenkov, Yury,Cordes, David B.,Slawin, Alexandra M. Z.,Cavallo, Luigi,Nahra, Fady,Cazin, Catherine S. J.,Nolan, Steven P.
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p. 601 - 611
(2017/12/26)
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- Phosphine ligand for indole skeleton as well as preparation method and application of phosphine ligand
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The invention provides a phosphine ligand for a 3-(disubstituted phosphino)-1-alkyl-2-substituted phenyl-indole skeleton as well as a preparation method and application of the phosphine ligand. The structure of the phosphine ligand for the 3-(disubstituted phosphino)-1-alkyl-2-substituted phenyl-indole skeleton is shown as the following formula I: (shown in the description), wherein Z is carbon or nitrogen, R is alkyl, substituted alkyl, olefin, aryl or fluorine, R1 is alkyl, substituted alkyl or aryl, R2 is alkyl, substituted alkyl or fluorine, and R3 is alkyl, substituted alkyl or aryl.
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Paragraph 0212; 0215; 0221-0225; 0227
(2017/12/30)
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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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- Palladium(II) Chloride Complexes of N,N′-Disubstituted Imidazole-2-thiones: Syntheses, Structures, and Catalytic Performances in Suzuki-Miyaura and Sonogashira Coupling Reactions
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Reactions of PdCl2 with 2 equiv of N,N′-disubstituted-imidazole-2-thiones R1R2C3N2S (R1 = R2 = Me (1a), iPr (1b), Cy (1c), C6Me3H2 (1d); R1 = Me, R2 = Ph (1e)) under the different conditions afford five mononuclear complexes trans-[(R1R2C3N2S)2PdCl2] (R1 = R2 = Me (2a), iPr (2b), Cy (2c), C6Me3H2 (2d); R1 = Me, R2 = Ph (2e)) and five binuclear Pd(II) complexes [(PdCl2){μ-(R1R2C3N2S)}]2 (R1 = R2 = Me (3a), iPr (3b), Cy (3c), C6Me3H2 (3d); R1 = Me, R2 = Ph (3e)), respectively. Complexes 2a-2e are easily converted into the corresponding 3a-3e by adding equimolar PdCl2 in refluxing MeOH, while the reverse reaction is achieved at room temperature by addition of 2 equiv of 1a-1e. In 2b, 2d, and 2e, each Pd(II) holds a distorted square planar geometry completed by two trans Cl atoms and two trans S atoms. Complexes 3a-3e have a dimeric [Pd2S2] structure in which two {PdCl2} units are interlinked by two N,N′-disubstituted-imidazole-2-thiones. Each Pd(II) adopts a distorted square planar geometry accomplished by two cis Cl atoms and two cis bridging S atoms. Among them, complex 3d has the two largest C6Me3H2 groups on the 2 and 5 positions of imidazole-2-thione, the longest Pd-μ-S bond, the largest S-Pd-S angle, and displays the highest catalytic activity toward Suzuki-Miyaura and copper-free Sonogashira cross-coupling reactions, which are confirmed by density functional theory calculations. The results provide an interesting insight into the introduction of various substituent groups into the periphery ligands of coordination complex-based catalysts, which could tune their geometric structures to acquire the best catalytic activity toward organic reactions.
- Zhang, Li-Ming,Li, Hai-Yan,Li, Hong-Xi,Young, David James,Wang, Yong,Lang, Jian-Ping
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p. 11230 - 11243
(2017/09/25)
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- A Zwitterionic Palladium(II) Complex as a Precatalyst for Neat-Water-Mediated Cross-Coupling Reactions of Heteroaryl, Benzyl, and Aryl Acid Chlorides with Organoboron Reagents
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The Suzuki–Miyaura cross-coupling (SMC) reactions of several heteroaryl chlorides, benzyl chlorides, and aryl acid chlorides with (hetero)arylboron reagents have been investigated in the presence of [Pd(HL1)(PPh3)Cl2] (I) [HL1 = 3-[(2,6-diisopropylphenyl)-1-imidazolio]-2-quinoxalinide] as catalyst and K2CO3 as base in neat water. The synthesis of the heterocycle-containing biaryls required the addition of 2 mol-% of a phosphine ligand (PPh3 or X-Phos). A combination of more than 115 substrates were screened and it was found that I is a versatile catalyst that can produce heterocycle-containing biaryls, diarylmethanes, and benzophenones in moderate-to-excellent yields.
- Ramakrishna, Visannagari,Rani, Morla Jhansi,Reddy, Nareddula Dastagiri
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p. 7238 - 7255
(2018/01/01)
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- Palladium-phosphine compound in catalyzing the application of the Suzuki reaction
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The invention discloses an application of a palladium-phosphine compound to catalysis of Suzuki reaction. The palladium-phosphine compound serving as a catalyst is capable of efficiently catalyzing Suzuki reaction in ethyl alcohol. By virtue of the palladium-phosphine compound, the defects of aqueous phase reaction are overcome; the aqueous phase reaction can be carried out in the presence of an extremely low quantity of catalysts; the palladium-phosphine compound is high in applicability to substrate; the Suzuki reaction can be carried out in the pollution-free environment in the presence of a relatively small quantity of catalysts.
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Paragraph 0098-0101
(2017/02/02)
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- Versatile palladium(II)-catalyzed Suzuki-Miyaura coupling in ethanol with a novel, stabilizing ligand
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Suzuki-Miyaura coupling reactions of arylboronic acids with aryl bromides were mediated by PdCl2 and bdppmapy (N,N-bis-(diphenylphosphanylmethyl)-2-aminopyridine) that both stabilizes and solubilizes the catalyst in predominantly ethanol as a solvent. Excellent yields for a wide variety of substrates were obtained under relatively mild conditions in this 'green' solvent.
- Ning, Jin-Jiao,Wang, Jian-Feng,Ren, Zhi-Gang,Young, David James,Lang, Jian-Ping
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p. 4000 - 4006
(2015/06/02)
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- A palladium catalyst supported on carbon-coated cobalt nanoparticles-preparation of palladium-free biaryls by suzuki-miyaura reactions in ethanol
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The preparation of a heterogeneous Pd catalyst supported on carbon-coated magnetic nanoparticles (NPs) bearing 4-(diphenylphosphinomethyl)phenyl groups is discussed. These NPs were initially prepared by chemical vapour deposition (CVD) of carbon on prefor
- Derible, Antoine,Diebold, Carine,Dentzer, Joseph,Gadiou, Roger,Becht, Jean-Michel,Le Drian, Claude
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supporting information
p. 7699 - 7706
(2015/04/22)
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- 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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- Nickel-catalyzed one-pot Suzuki-Miyaura cross-coupling of phenols and arylboronic acids mediated by N,N-ditosylaniline
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An efficient method for the construction of two distinct C aryl-Caryl bonds through the Ni-catalyzed Suzuki-Miyaura cross-coupling of phenols with arylboronic acids has been developed. This reaction proceeds through the in situ tosylation of phenols by using N,N-ditosylaniline as the sulfonylating reagent, which is highly active, markedly stable, and easily prepared. The scope with respect to the coupling partners - phenols and boronic acids - is broad, and sensitive functional groups are tolerated. Phenols, especially those containing an unprotected amino group, which are generally problematic for coupling under conventional one-pot conditions, are also viable substrates in this transformation.
- Chen, Liangshun,Lang, Hongyue,Fang, Lei,Zhu, Mengyun,Liu, Jinqian,Yu, Jianjun,Wang, Limin
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supporting information
p. 4953 - 4957
(2014/08/18)
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- A simple catalytic system based on PdCl2(CH3CN) 2 in water for cross-coupling reactions using diazonium salts
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Aryl-heteroaryl and heteroaryl-heteroaryl compounds are obtained through the Suzuki-Miyaura cross-coupling reactions between diazonium salts and potassium trifluoroborates using PdCl2(CH3CN)2 as the catalyst in water and in the absence of any additive, ligand or base. In addition, the same mild catalytic system is effective for the Matsuda-Heck reaction between several monoolefins with aryldiazonium salts.
- El Bakouri, Ouissam,Fernández, Martí,Brun, Sandra,Pla-Quintana, Anna,Roglans, Anna
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p. 9761 - 9765
(2013/10/22)
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- Nickel-catalyzed Suzuki-Miyaura coupling of heteroaryl ethers with arylboronic acids
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Nickel-catalyzed Suzuki-Miyaura coupling of heteroaryl ethers with arylboronic acids was described. Selective activation of the phenol C-O bonds was achieved by converting them into the corresponding aryl 2,4-dimethoxy-1,3,5- triazine-6-yl ethers, in which aryl C-O bond could be selectively cleaved with inexpensive, air-stable NiCl2(dppf) as a catalyst. Coupling of these readily accessible heteroaryl ethers proved tolerant of extensive functional groups.
- Li, Xiao-Jian,Zhang, Jin-Ling,Geng, Yu,Jin, Zhong
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p. 5078 - 5084
(2013/06/27)
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- C,N-palladacycles containing N-heterocyclic carbene and azido ligands - Effective catalysts for Suzuki-Miyaura cross-coupling reactions
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Azido-palladacycles containing C,N-donor and N-heterocyclic carbene ligands, [(C,N-L)Pd(N3)(NHC)] [NHC = IPr; 1,3-bis(2,6- diisopropylphenyl)imidazol-2-ylidene], were prepared from (i) IPr and dinuclear PdII azides, [Pd(μ-N3)(C,N-Ln)]2 [C,N-L1H = N,N′-dimethylbenzylamine; C,N-L2H = 2-(2′-thienyl)pyridine; C,N-L3H = azobenzene; C,N-L 4H = 2-(p-tolyl)pyridine], or from (ii) NaN3 and mononuclear PdII chloride, [Pd(Cl)(IPr)(C,N-Ln)], in aqueous solution. The structures of two of these products were determined by X-ray crystallography. The palladacycles showed high catalytic efficiency toward activated and nonactivated aryl bromides (at room temperature) as well as aryl chlorides (at 80 C) in Suzuki-Miyaura cross-coupling reactions. In addition, coupling reactions of aryl chlorides using potassium aryl trifluoroborates instead of phenyl boronic acid gave good-to-excellent product yields. Suzuki-Miyaura cross-coupling reactions of aryl bromides and chlorides with organoboronic acid as well as potassium aryl trifluoroborates catalyzed by C,N-donor palladacycles containing N-heterocyclic carbene (NHC) and azido ligands under various conditions have been performed. Copyright
- Kim, Yong-Joo,Lee, Jung-Hyun,Kim, Taejung,Ham, Jungyeob,Zheng, Zhen Nu,Lee, Soon W.
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p. 6011 - 6017
(2013/03/14)
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- Palladium nanoparticles in Suzuki cross-couplings: Tapping into the potential of tris-imidazolium salts for nanoparticle stabilization
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Inspired by the proclivity of various palladium sources to form nanoparticles in imidazolium-based ionic liquids, we now report that tris-imidazolium salts bearing hexadecyl chains and a bridging mesitylene moiety are potent stabilizers of palladium nanoparticles efficiently prepared via a Chaudret-type hydrogenation of the bis(dibenzylideneacetone)palladium(0). The palladium nanoparticles have been isolated in pure form and characterized by 1H nuclear magnetic resonance, transmission electron microscopy, electron diffraction and dynamic light scattering. The new materials proved effective in Suzuki cross-coupling at a loading of 0.2% palladium. Thus, using a tris-imidazolium iodide-palladium material, a series of biaryl products has been prepared starting from aryl bromides and some activated chlorides. The possibility that this catalytic activity might be due to the formation of palladium N-heterocyclic carbenes has been addressed through solid state 13C NMR and the synthesis of an imidazolium analogue in which the acidic 2-H was replaced with a methyl group. Copyright
- Planellas, Marc,Pleixats, Roser,Shafir, Alexandr
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supporting information; experimental part
p. 651 - 662
(2012/05/04)
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- Design, synthesis and biological evaluation of 5-hydroxy, 5-substituted-pyrimidine-2,4,6-triones as potent inhibitors of gelatinases MMP-2 and MMP-9
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Matrix metalloproteinases (MMPs) are attractive biological targets that play a key role in many physiopathological processes such as degradation of extracellular matrix proteins, release and cleavage of cell-surface receptors, tumour progression, homeostatic regulation and innate immunity. A series of 5-hydroxy, 5-substituted pyrimidine-2,4,6-triones were rationally designed, prepared and tested as inhibitors of gelatinases MMP-2 and MMP-9 and collagenase MMP-8. On one side, the presence of the 5-hydroxyl group, that represents an typical feature of this class of compounds, ensured an attractive pharmacokinetic profile while on the other suitably substituted biaryl molecular fragments, attached to position 5 through a ketomethylene linker, guaranteed favourable interaction in the deep region of the S1′ enzymatic subsite. This rational design led to the discovery of highly potent MMP inhibitors. In particular, biphenyl derivatives bearing at the para position COCH3 and OCF3 substituents permitted to inhibit gelatinases MMP-2 and MMP-9, with IC50 values as low as 30 nM and 21 nM, respectively, whereas the introduction at the same position of the bulkier SO2CH3 group afforded a potent collagenase MMP-8 inhibitor with an IC50 value equal to 66 nM. Molecular docking simulations allowed us to elucidate key interactions driving the binding of the top active compounds towards their preferred MMP target.
- Nicolotti, Orazio,Catto, Marco,Giangreco, Ilenia,Barletta, Maria,Leonetti, Francesco,Stefanachi, Angela,Pisani, Leonardo,Cellamare, Saverio,Tortorella, Paolo,Loiodice, Fulvio,Carotti, Angelo
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p. 368 - 376
(2013/02/22)
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- General and highly efficient fluorinated-N-heterocyclic carbene-based catalysts for the palladium-catalyzed Suzuki-Miyaura reaction
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A general and highly efficient trifluoromethylated-N-heterocyclic carbene (NHC)-based catalyst for the palladium-catalyzed Suzuki-Miyaura reaction was reported. In the presence of the catalyst, reactions of non-activated aryl chlorides and triflates with aryl boronic acids occurred at room temperature with good to excellent yields (63-98%). In addition, catalysts generated from a combination of Pd(OAc)2/imidazolium salt 6a is not only effective for the coupling of heteroaryl boronic acid with aryl halides and heteroaryl halides, but also efficient for coupling of other heteroaryl halides and heteroaryl boronic acids. Finally, the catalyst is highly effective for Suzuki-Miyaura reaction of aryl bromides and chlorides with 0.01-0.1 mol % loading if the temperature was raised at refluxed THF/H2O.
- Liu, Taoping,Zhao, Xiaoming,Shen, Qilong,Lu, Long
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supporting information; experimental part
p. 6535 - 6547
(2012/08/28)
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- Palladium nanoparticles in ionic liquid by sputter deposition as catalysts for suzuki-miyaura coupling in water
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Palladium nanoparticles in an ionic liquid prepared readily by sputter deposition efficiently catalyze the Suzuki-Miyaura coupling of hydrophobic as well as hydrophilic aryl halides in water.
- Oda, Yoshiro,Hirano, Koji,Yoshii, Kazuki,Kuwabata, Susumu,Torimoto, Tsukasa,Miura, Masahiro
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supporting information; experimental part
p. 1069 - 1071
(2011/01/09)
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- Perfluoro-tagged, phosphine-free palladium nanoparticles supported on silica gel: Application to alkynylation of aryl halides, Suzuki-Miyaura cross-coupling, and Heck reactions under aerobic conditions
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The utilization of perfluoro-tagged palladium nanoparticles immobilized on fluorous silica gel through fluorous-fluorous interactions (Pd np-A/FSG) or through covalent bonding to silica gel (Pd np-B) in the alkynylation of aryl halides, in the Suzuki-Miyaura cross-coupling, as well as in the Heck reaction between methyl acrylate and aryl iodides is described. The reactions are carried out under aerobic and phosphine-free conditions with excellent to quantitative product yields in each case. The catalysts are easily recovered and reused several times without significant loss of activity. The alkynylation of aryl halides (under copper-free conditions) and the Suzuki-Miyaura cross-coupling are carried out in water. The Heck reaction of methyl acrylate with aryl iodides is best performed in MeCN. The utilization of Pdnp-B in the synthesis of 2,3-disubstituted indoles from 2-(alkynyl)trifluoroacetanilides and aryl halides is also reported.
- Bernini, Roberta,Cacchi, Sandro,Fabrizi, Giancarlo,Forte, Giovanni,Petrucci, Francesco,Prastaro, Alessandro,Niembro, Sandra,Shafir, Alexandr,Vallribera, Adelina
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supporting information; experimental part
p. 150 - 158
(2010/05/18)
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- Highly efficient reusable polymer-supported Pd catalysts of general use for the Suzuki reaction
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Short and efficient syntheses of various polymer-supported Pd catalysts are reported. The reactivity of these catalysts has been determined for the Suzuki reaction. It turned out that the (tert-butylphenylphosphinomethyl)polystyrene-supported Pd catalyst 2′a is highly efficient for versatile Suzuki reactions from aryl chlorides. These couplings are performed in the presence of low amounts (4 mequiv) of supported Pd, the catalyst can be reused more than seven times without loss of efficiency and the Pd leaching is extremely low (0.1% of the initial amount).
- Schweizer, Stéphane,Becht, Jean-Michel,Le Drian, Claude
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experimental part
p. 765 - 772
(2010/09/07)
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- Palladium/tetraphosphine catalyzed suzuki cross-coupling of heteroarylboronic acids with aryl halides
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(Chemical Equation Presented) cis,cis,cis-1,2,3,4- Tetrakis(diphenylphosphinomethyl)cyclopentane/[PdCl(C3H 5)]2 efficiently catalyses the Suzuki reaction of heteroarylboronic acids with aryl bromides and also the coupling of arylboronic acids with heteroaryl bromides. The coupling of thiophene- or benzothiopheneboronic acids, furan- or benzofuranboronic acids and 3-pyridineboronic acid with a variety of aryl bromides gave the corresponding coupling products in good yields. However, in most cases, better results in terms of ratio substrate/catalyst were obtained for the reverse reaction using heteroaryl bromides with arylboronic acids.
- Kondolff, Isabelle,Doucet, Henri,Santelli, Maurice
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p. 109 - 118
(2008/09/18)
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- Highly efficient and reusable supported Pd catalysts for Suzuki-Miyaura reactions of aryl chlorides
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Syntheses of air- and moisture-stable heterogeneous (tert- butylarylphosphino)polystyrene-supported Pd catalysts and their use for versatile Suzuki-Miyaura reactions of aryl chlorides and arylboronic acids under non-anhydrous conditions are reported. The catalysts are easily recovered by filtration. They can be used many times (more than seven) without showing any loss of activity, and the amount of Pd leached is extremely low (0.1%).
- Schweizer, Stephane,Becht, Jean-Michel,Le Drian, Claude
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p. 3777 - 3780
(2008/02/12)
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- Microwave-promoted Suzuki coupling reactions with organotrifluoroborates in water using ultra-low catalyst loadings
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The Suzuki reaction in water using parts per million concentrations of palladium is reported using potassium trifluoroborates as alternatives to boronic acids as substrates.
- Arvela, Riina K.,Leadbeater, Nicholas E.,Mack, Tamera L.,Kormos, Chad M.
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p. 217 - 220
(2007/10/03)
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- Suzuki coupling reactions of heteroarylboronic acids with aryl halides and arylboronic acids with heteroaryl bromides using a tetraphosphine/palladium catalyst
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cix,cis,cis-1,2,3,4-Tetrakis(diphenylphosphinomethyl)cyclopentane/ [PdCl(C3H5)]2 efficiently catalyses the Suzuki reaction of heteroarylboronic acids with aryl bromides and also the coupling of arylboronic acids with heteroaryl bromides. The coupling of thiopheneboronic acids, 3-furanboronic acid and 3-pyridineboronic acid with a variety of aryl bromides gave the corresponding adducts in good yields. However, in most cases, better results in terms of substrate/catalyst ratio were obtained for the reaction of heteroaryl bromides with arylboronic acids. Georg Thieme Verlag Stuttgart.
- Kondolff, Isabelle,Doucet, Henri,Santelli, Maurice
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p. 2057 - 2061
(2007/10/03)
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- Combining enabling techniques in organic synthesis: Solid-phase-assisted catalysis under microwave conditions using a stable Pd(II)-precatalyst
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The catalytic activity of a 2-pyridinealdoxime-based Pd(II)-complex covalently anchored via the oxime moiety to a glass/polymer composite material was evaluated in Suzuki-Miyaura cross-coupling reactions of aryl and heteroaryl halides, including arylchlorides, with aryl and heteroaryl boronic acids both under thermal as well as microwave irradiating conditions in water. The stability and reusability of this Pd-precatalyst is part of the present study.
- Dawood, Kamal M.,Kirschning, Andreas
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p. 12121 - 12130
(2007/10/03)
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- METHOD FOR CARRYING OUT CHEMICAL REACTIONS INVOLVING COMPOUNDS ADSORBED ON FLUORINATED CARRIER MATERIALS BY MEANS OF FLUORINE-FLUORINE INTERACTIONS
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The invention relates to a method for carrying out a chemical reaction of a compound (B), involving a compound (A-F) which is adsorbed on a fluorinated carrier material (FT) by means of fluorine-fluorine interactions, forming an addition compound (A-F):(FT). The inventive method is characterised in that said addition compound (A-F):(FT) is suspended in a suitable solvent containing the compound B, whereby said compound B is reacted to form the reaction product B', in the presence of the adsorbed compound A-F.
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Page/Page column 25-26; 28
(2008/06/13)
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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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p. 4500 - 4503
(2007/10/03)
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- Synthesis of unsymmetrical biaryls by electroreductive cobalt-catalyzed cross-coupling of aryl halides
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The consumable anode process allows the electrochemical cross-coupling reaction between various functionalized aromatic halides (iodides, bromides and chlorides) in the presence of cobalt halides as catalyst in a mixed solvent acetonitrile/pyridine (9:1). A great variety of unsymmetrical biaryls are obtained in moderate to excellent yields.
- Gomes, Paulo,Fillon, Hyacinthe,Gosmini, Corinne,Labbé, Eric,Périchon, Jacques
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p. 8417 - 8424
(2007/10/03)
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- Synthesis and cross-coupling reactions of tetraalkylammonium organotrifluoroborate salts
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Treatment of organoboronic acids with hydrofluoric acid generates an in situ tetracoordinate hydronium organotrifluoroborate species which undergoes counterion exchange with tetra-n-butylammonium hydroxide. The resultant tetraalkylammonium salts are as air and moisture stable as their potassium organotrifluoroborate counterparts with the added advantage of being readily soluble in organic media. They were found to undergo Pd-catalyzed Suzuki-Miyaura cross-couplings with a variety of aryl- and alkenylhalides under mild conditions. Their Pd-catalyzed cross-coupling with acid halides is also possible for the generation of ketones.
- Batey, Robert A,Quach, Tan D
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p. 9099 - 9103
(2007/10/03)
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- Biaryls via suzuki cross-couplings catalyzed by nickel on charcoal
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Using the heterogeneous catalyst 'Ni/C', biaryl bonds can be made between functionalized aryl chlorides and boronic acids in good isolated yields. A standard set of conditions has been developed which applies to a variety of reaction partners. (C) 2000 Elsevier Science Ltd.
- Lipshutz, Bruce H.,Sclafani, Joseph A.,Blomgren, Peter A.
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p. 2139 - 2144
(2007/10/03)
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- Direct Preparation of 3-Thienyl Organometallic Reagents: 3-Thienylzinc and 3-Thienylmagnesium Iodides and 3-Thienylmanganese Bromides and Their Coupling Reactions
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3-Thienylzinc and 3-thienylmagnesium iodides can be generated from the direct oxidative addition of Rieke zinc and magnesium to 3-iodothiophene, respectively. The direct preparation of 3-thienylmanganese bromides from the reaction of Rieke manganese with 3-bromothiophene and 3,4-dibromothiophene is also performed. These 3-thienyl organometallic reagents have been found to be regiostable intermediates and undergo coupling reactions with a variety of versatile electrophiles such as acid chlorides, aryl iodides, aldehydes, and disulfide.
- Rieke, Reuben D.,Kim, Seung-Hoi,Wu, Xiaoming
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p. 6921 - 6927
(2007/10/03)
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