- A re-evaluation of the photophysical properties of 1,4-bis(phenylethynyl)benzene: A model for poly(phenyleneethynylene)
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Photophysical measurements, recorded in aerated cyclohexane at 283 K, indicate that 1,4-bis-(phenylethynyl)benzene behaves in a conventional manner, undergoing emission from the lowest vibrational level of the first excited singlet state; there is no evid
- Beeby, Andrew,Findlay, Karen,Low, Paul J.,Marder, Todd B.
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Read Online
- Choline chloride/CuCl as an effective homogeneous catalyst for palladium-free Sonogashira cross-coupling reactions
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Choline chloride-CuCl (ChCl-CuCl) has been employed as an efficient catalytic system in the palladium-free Sonogashira-type cross-coupling reactions of phenylacetylene with a variety of aryl halides. Choline chloride, as an effective ligand and a quaterna
- Hajipour, Abdol R.,Nazemzadeh, Seyed Hadi,Mohammadsaleh, Fatemeh
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Read Online
- From branched hydrocarbon propellers to C3-symmetric graphite disks
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Branched hydrocarbon propellers (9 and 12) were prepared by stepwise palladium-catalyzed Hagihara-Sonogashira coupling reactions and Diels-Alder cycloadditions and submitted to oxidative cyclodehydrogenation by FeCl 3 to afford two new giant graphite disks 2 and 3 with 3-fold symmetry in high yield. One of the precursors, the polyphenylene dendrimer 9 containing 150 carbon atoms, was crystallographically characterized. The poorly soluble graphite disks were characterized by isotope-resolved MALDI-TOF mass spectroscopy, and their electronic and vibrational properties were investigated by solid-state UV-vis and Raman spectroscopy. The effect of molecular size and geometry on their properties was discussed. The molecule 2 represents the largest, 3-fold-symmetric all-benzenoid graphite disk, and the five-membered rings in molecule 3 open the opportunity to synthesize large bowl-shaped PAHs.
- Wu, Jishan,Tomovic, Zeljko,Enkelmann, Volker,Muellen, Klaus
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Read Online
- Facile one-pot synthesis of diarylacetylenes from arylaldehydes: Via an addition-double elimination process
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A practical one-pot protocol has been developed to synthesize diarylacetylenes from arylaldehydes by treatment with 1-(arylmethyl)benzotriazoles and LiN(SiMe3)2. The reaction proceeded through imine formation, Mannich-type addition and double elimination to deliver products in up to 99% yields with broad substrate scope. In addition, gram-scale synthesis of 1-bromo-4-(phenylethynyl)benzene has been demonstrated.
- Chen, Jianyang,Zhang, Xuan,Wu, Jiajun,Wang, Rui,Lei, Chunlin,An, Yanan
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p. 4701 - 4705
(2021/06/11)
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- Immobilized Pd on a NHC-functionalized metal-organic FrameworkMIL-101(Cr): An efficient heterogeneous catalyst in the heck and copper-free Sonogashira coupling reactions
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A heterogeneous palladium catalyst system based on immobilization of palladium moieties on a N-heterocyclic carbene (NHC) modified metal organic framework (MOF) was developed for the Heck and copper-free Sonogashira coupling reactions. In order to prepare this catalyst system, first, MIL-101(Cr) was functionalized with NHC moieties through a post synthetic modification (PSM) approach, and then Pd metal was stabilized on the prepered MIL-101(Cr)-NHC substrate. This material was characterized using various microscopic and spectroscopic techniques and then was used as an efficient heterogeneous Pd catalyst system in the Heck and copper-free Sonogashira reactions. Results of the heterogeneity tests showed that the Pd-NHC-MIL-101(Cr) catalyst can efficiently catalyzed these coupling reactions heterogeneously and no remarkable changes observed in the morphology and structure of MIL-101(Cr) template during the reaction progress. Also, existence of palladium nanoparticles immobilized on the MOF structure affirmed by the TEM and XPS analysis confirmed the oxidation state of Pd. A variety of alkene and alkyne derivatives were synthesized in good to excellent yields using this heterogeneous Pd catalyst system under normal conditions. More importantly Pd-NHC-MIL-101(Cr) catalyst was simply recovered from the reaction medium without remarkable decreasing in its catalytic activities after five times of reusability. The ICP analysis showed the very low Pd and Cr metals leaching, representing high stability and applicability of this catalyst in Pd coupling reactions.
- Niknam, Esmaeil,Panahi, Farhad,Khalafi-Nezhad, Ali
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supporting information
(2021/01/12)
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- Decorated palladium nanoparticles on mesoporous organosilicate as an efficient catalyst for Sonogashira coupling reaction
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Abstract: Reforming mesoporous silica was provided by the reaction of SBA‐15 with (3-aminopropyl)triethoxysilane, the product of which was treated with furfural to give SBA-propyl-imine-furan. In the next step, palladium chloride was attached to the funct
- Mohajer, Fatemeh,Mohammadi Ziarani, Ghodsi,Badiei, Alireza
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p. 589 - 601
(2020/09/17)
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- Selective Synthesis of Non-Aromatic Five-Membered Sulfur Heterocycles from Alkynes by using a Proton Acid/N-Chlorophthalimide System
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A multicomponent strategy to achieve two different regioselectivities from alkynes, isothiocyanates and H2O with a proton acid/N-chlorophthalimide (NCPI) system is described to selectively obtain non-aromatic five-membered sulfur heterocycles (1,3-oxathiol-2-imines/thiazol-2(3H)-one derivatives) through multiple bond formations. The process features readily available starting materials, mild reaction conditions, broad substrate scope, good functional-group tolerance, high regio- and chemo- selectivities, gram-scale synthesis and late-stage modifications. Mechanistic studies support the proposal that the transformation process includes a combination of H2O and isothiocyanate, free-radical formation, carbonation and intramolecular cyclization to give the products. Furthermore, the 1,3-oxathiol-2-imine derivatives possess unique fluorescence characteristics and can be used as Pd2+ sensors with a “turn-off” response, demonstrating potential applications in environmental and biological fields.
- Yu, Wentao,Zhu, Baiyao,Shi, Fuxing,Zhou, Peiqi,Wu, Wanqing,Jiang, Huanfeng
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supporting information
p. 1313 - 1322
(2020/12/01)
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- Simple and efficient diaryl alkyne synthesis method
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The embodiment of the invention discloses a simple and efficient diaryl alkyne synthesis method. The method comprises the steps of by taking arylmethylbenzotriazole and aromatic aldehyde as raw materials, carrying out addition and double-beta-elimination reaction under the action of bis (trimethylsilyl) amino salt MN (SiMe3) 2 to synthesize diaryl alkyne by a one-pot method. The raw materials and chemical reagents used in the method are easy to obtain, the reaction conditions are mild, the operation is simple, the substrate universality is good, the product yield is high, and the method is a simple and efficient diaryl alkyne synthesis method.
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Paragraph 0026; 0029-0031
(2021/04/14)
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- Cu2O Nanocrystals-Catalyzed Photoredox Sonogashira Coupling of Terminal Alkynes and Arylhalides Enhanced by CO2
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Herein the first visible-light-activated Sonogashira C?C coupling reaction at room temperature catalyzed by single-metal heterogeneous Cu2O truncated nanocubes (Cu2O TNCs) was developed. A wide variety of aryl halides and terminal alkynes worked well in this recyclable heterogeneous photochemical process to form the corresponding Sonogashira C?C coupling products in good yields. Mechanistic control studies indicated that CO2 enhances the formation of light-absorbing heterogeneous surface-bound CuI-phenylacetylide (λmax=472 nm), which further undergoes single-electron transfer with aryl iodides/bromides to enable Sonogashira Csp2 ?Csp bond formation. In contrast to literature-reported bimetallic TiO2-containing nanoparticles as photocatalyst, this work avoided the need of cocatalysis by TiO2. Single-metal CuI in Cu2O TNCs was solely responsible for the observed Csp2 ?Csp coupling reactions under CO2 atmosphere.
- Shanmugam, Munusamy,Sagadevan, Arunachalam,Charpe, Vaibhav Pramod,Pampana, V. Kishore Kumar,Hwang, Kuo Chu
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p. 287 - 292
(2019/11/05)
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- Arylation of Terminal Alkynes by Aryl Iodides Catalyzed by a Parts-per-Million Loading of Palladium Acetate
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Arylation of terminal alkynes (16 varieties) by aryl iodides (28 varieties) was achieved with a mol ppm loading level of palladium catalyst, where a variety of functional groups including heteroarenes were tolerated. Thus, the arylations were carried out in the presence of palladium acetate at ppm loadings and potassium carbonate in ethanol at 80 °C to give the corresponding internal alkynes in good to excellent yields. Synthesis of 2-phenyl-3-(phenylalkynyl)benzofuran was achieved by iterative use of the alkyne arylation under mol ppm catalytic conditions. Reaction-rate analysis, transmission electron microscopic (TEM) examination of the reaction mixture, and mercury-amalgamation test were performed to gain insight into the active species of the highly active ppm catalytic species. TEM examination of the reaction mixture revealed that palladium nanoparticles were generated in situ under the reaction conditions, and their cluster size was variable during the catalytic reaction. A variation in size of palladium particles suggested that the composition-decomposition process of Pd aggregates should take place in situ via monomeric palladium(0) species and/or fine palladium(0) clusters, which might be real catalytic species in this reaction.
- Hamasaka, Go,Roy, David,Tazawa, Aya,Uozumi, Yasuhiro
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p. 11640 - 11646
(2019/12/02)
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- Sulfo-Phenylated Polyphenylenes Containing Sterically Hindered Pyridines
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We systematically investigated the effect of incorporating a sterically hindered pyridyl group into a sulfo-phenylated polyphenylene to control the polymer's physicochemical properties through acid-base interactions. Homopolymers with similar molecular weights and comparable structures that vary by only one atom (N- vs C-) per repeat unit along the polymer chain were prepared. Compared to a non-pyridyl reference membrane, incorporation of a pyridyl group improves the oxidative stability against free radicals, increases the elongation at break to 55% (from 37%), and enhances the thermal stability to 326 °C (from 246 °C). In an accelerated fuel cell degradation test, polymeric membranes containing the sterically encumbered pyridyl unit exhibited exceptional stability (0.16 mV h-1 degradation rate over 1000 h) and retained ~80% of their peak power density over this time.
- Xu, Shaoyi,Adamski, Michael,Killer, Miho,Schibli, Eric M.,Frisken, Barbara J.,Holdcroft, Steven
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p. 2548 - 2559
(2019/03/26)
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- Sequentially Pd/Cu-Catalyzed Alkynylation-Oxidation Synthesis of 1,2-Diketones and Consecutive One-Pot Generation of Quinoxalines
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We report a simple and efficient one-pot synthesis of 1,2-diketones by concatenation of two Pd/Cu-catalyzed processes: Pd0/CuI-catalyzed Sonogashira coupling of terminal alkynes with aryl (pseudo)halides furnishes internal alkynes, which are directly transformed by PdII/CuII-catalyzed Wacker-type oxidation with DMSO and oxygen as dual oxidants to furnish 1,2-diketones. With this efficient, catalyst economical process, various aryl iodides and triflates are efficiently transformed in high yields into symmetrically and unsymmetrically substituted 1,2-diketones with various functional groups. This process can be readily extended to a consecutive one-pot synthesis of quinoxalines in a diversity-oriented fashion.
- Niesobski, Patrik,Martínez, Ivette Santana,Kustosz, Sebastian,Müller, Thomas J. J.
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supporting information
p. 5214 - 5218
(2019/07/31)
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- Supramolecular photocatalyst of Palladium (II) Encapsulated within Dendrimer on TiO2 nanoparticles for Photo-induced Suzuki-Miyaura and Sonogashira Cross-Coupling reactions
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In this study, synthesis, characterization and catalytic performance of a novel supramolecular photocatalytic system including palladium (II) encapsulated within amine-terminated poly (triazine-triamine) dendrimer modified TiO2 nanoparticles (Pd (II) [PTATAD] @ TiO2) is presented. The obtained nanodendritic catalyst was characterized by FT-IR, ICP-AES, XPS, EDS, TEM, TGA and UV-DRS. The as-prepared nanodendritic catalyst was shown to be highly active, selective, and recyclable for the Suzuki–Miyaura and Sonogashira cross-coupling of a wide range of aryl halides including electron-rich and electron-poor and even aryl chlorides, affording the corresponding biaryl compounds in good to excellent yields under visible light irradiation. This study shows that visible light irradiation can drive the cross-coupling reactions on the Pd (II) [PTATAD] @ TiO2 under mild reaction conditions (27–30?°C) and no additional additives such as cocatalysts or phosphine ligands. So, we propose that the improved photoactivity predominantly benefits from the synergistic effects of Pd (II) amine-terminated poly (triazine-triamine) dendrimer on TiO2 nanoparticles that cause efficient separation and photogenerated electron–hole pairs and photoredox capability of nanocatalyst which all of these advantages due to the tuning of band gap of catalyst in the visible light region.
- Eskandari, Ameneh,Jafarpour, Maasoumeh,Rezaeifard, Abdolreza,Salimi, Mehri
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- Catalytic Activation of Trimethylsilylacetylenes: A One-Pot Route to Unsymmetrical Acetylenes and Heterocycles
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For the synthesis of unsymmetrical acetylenes, a Sonogashira coupling-deprotection-Sonogashira coupling reaction sequence is often used. Removal of protecting groups requires harsh conditions or an excess of difficult to handle and expensive reagents. Herein, we disclose a novel catalytic method for the selective deprotection of trimethylsilylacetylenes in Sonogashira reaction. The reagent hexafluorosilicic acid, an inexpensive nontoxic compound, was used to promote the selective desilylation. This method enables the efficient synthesis of unsymmetric acetylenes with other silylated functional groups present. Further possibilities of the method were explored by synthesis of heterocycles.
- Lasányi, Dániel,Mészáros, ádám,Novák, Zoltán,Tolnai, Gergely L.
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p. 8281 - 8291
(2018/06/11)
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- Palladium Niacin Complex Immobilized on Starch-Coated Maghemite Nanoparticles as an Efficient Homo- and Cross-coupling Catalyst for the Synthesis of Symmetrical and Unsymmetrical Biaryls
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Abstract: In this work, catalytic efficiency of palladium niacin complex immobilized on starch-coated maghemite nanoparticles successfully exploited for homo- and cross-coupling reactions such as Suzuki–Miyaura, Sonogashira-, and Ullmann coupling reactions. The solid catalyst characterized by different methods such as FT-IR, TGA, XPS, EDS and ICP-AES. TEM images revealed a nanosize structure for catalyst and vibrating sample magnetometer (VSM) demonstrated its magnetic property. The reactions proceeded well in the absence of commonly used additives with high selectivity. Potential reusability of magnetically separable palladium catalyst and performing the reactions at environmentally conditions are notable features of the present methods making great potential for practical applications. Graphical Abstract: [Figure not available: see fulltext.].
- Rezapour, Elham,Jafarpour, Maasoumeh,Rezaeifard, Abdolreza
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p. 3165 - 3177
(2018/08/22)
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- Ferrocenyl bisoxazoline as an efficient non-phosphorus ligand for palladium-catalyzed copper-free Sonogashira reaction in aqueous solution
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Pd(OAc)2-catalyzed Sonogashira coupling reactions of alkynes and a variety of aryl halides with 1,3-bis(5-ferrocenylisoxazoline-3-yl)benzene as an efficient non-phosphorus ligand under copper-free conditions are presented. The main advantages over previous methodologies include low catalyst loading (0.2 mol% Pd(OAc)2 and 0.4 mol% ferrocenyl bisoxazoline ligand are sufficient for these coupling reactions), less problematic reaction medium (water–dimethylformamide) and more convenient operation (no requirement for nitrogen protection).
- Yu, Shuyan,Wu, Jingxin,He, Xinwei,Shang, Yongjia
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- Palladium(II) complex for catalyzing sonogashira coupling reactions and a method thereof
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A palladium(II) complex which catalyzes the Sonogashira coupling reaction efficiently under aerobic condition and a method of employing the palladium(II) complex to synthesize internal alkynes. The palladium(II) complex is an effective catalyst for the co
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Page/Page column 21
(2017/02/09)
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- DNA-supported palladium nanoparticles as a reusable catalyst for the copper- and ligand-free Sonogashira reaction
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DNA nanotechnology has recently emerged as a powerful discipline with diverse applications. However, studies focused on the combination of DNA and metal nanoparticles for catalyst design are scanty. We have prepared a catalyst composed of palladium nanoparticles supported on DNA which has been characterised by TEM, SEM, EDX, UV, FTIR and XPS. The catalyst, mainly composed of Pd(ii) and Pd(iv) species in the form of oxides, has been effectual in the copper- and ligand-free Sonogashira-Hagihara coupling of aryl iodides with terminal aromatic and aliphatic alkynes. The products are obtained in 54-86% isolated yields using low catalyst loading (0.5 mol%) under mild conditions (65 °C) in methanol without air exclusion. Moreover, the catalyst can be easily recovered and reused in five cycles and shows better performance than an array of commercial palladium catalysts. The mechanistic aspects of the reaction are also tackled in detail.
- Camacho, Ana Silvia,Martín-García, Iris,Contreras-Celedón, Claudia,Chacón-García, Luis,Alonso, Francisco
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p. 2262 - 2273
(2017/07/24)
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- Synthesis of functionalized alkynes via palladium-catalyzed Sonogashira reactions
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A highly efficient protocol for the copper and phosphine free Sonogashira cross-coupling reactions of aryl iodides with terminal alkynes under aerobic conditions has been developed. Using 1 mol % of the palladium-bis(oxazoline) complex, Pd-BOX A, in the p
- Ibrahim, Mansur B.,Ali, Bassam El,Malik, Imran,Fettouhi, Mohammed
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p. 554 - 558
(2016/01/20)
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- Supported palladium nanoparticles-catalyzed decarboxylative coupling approaches to aryl alkynes, indoles and pyrrolines synthesis
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The polystyrene supported palladium (Pd@PS) nanoparticles (NPs) catalyzed decarboxylative coupling (DC) of arylhalides and alkynyl carboxylic acids was developed for the synthesis of diaryl alkynes. Indole and 3-pyrroline heterocycles were also synthesized from 2-iodo anilines/amino benzocycloheptene bromide and alkynyl carboxylic acids, following a domino decarboxylative coupling-cyclization (DCC) approach under the same catalytic conditions. The combined anchoring and catalytic behaviour of Pd@PS makes the process favourable for the product formation.
- Reddy, C. Bal,Bharti, Richa,Kumar, Sandeep,Das, Pralay
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p. 71117 - 71121
(2016/08/05)
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- Synthesis and characterization of a novel magnetic nano-palladium Schiff base complex: application in cross-coupling reactions
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A novel and task-specific nano-magnetic Schiff base ligand with phosphate spacer using 2-aminoethyl dihydrogen phosphate instead of usual coating agents, i.e. tetraethoxysilane and 3-aminopropyltriethoxysilane, for coating of nano-magnetic Fe3O4 is introduced. The nano-magnetic Schiff base ligand with phosphate spacer as a novel catalyst was synthesized and fully characterized using infrared spectroscopy, X-ray diffraction, scanning and transmission electron microscopies, thermogravimetry, derivative thermogravimetry, vibrating sample magnetometry, atomic force microscopy, X-ray photoelectron spectroscopy and energy-dispersive X-ray spectroscopy. The resulting task-specific nano-magnetic Schiff base ligand with phosphate spacer was successfully employed as a magnetite Pd nanoparticle-supported catalyst for Sonogashira and Mizoroki–Heck C–C coupling reactions. To the best of our knowledge, this is the first report of the synthesis and applications of magnetic nanoparticles of Fe3O4@O2PO2(CH2)2NH2 as a suitable spacer for the preparation of a designable Schiff base ligand and its corresponding Pd complex. So the present work can open up a new and promising insight in the course of rational design, synthesis and applications of various task-specific magnetic nanoparticle complexes.
- Aghayee, Millad,Zolfigol, Mohammad Ali,Keypour, Hassan,Yarie, Meysam,Mohammadi, Leila
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p. 612 - 618
(2016/07/19)
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- Boronate ester post-functionalization of PPEs: versatile building blocks for poly(2,2′-(1-(4-(1,2-di(thiophen-2-yl)vinyl)phenyl)-2-(2,5-dioctylphenyl)ethene-1,2-diyl)dithiophene) and application in field effect transistors
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A convenient and scalable strategy for post-functionalization of poly(phenylene-ethynylene)s and phenylene-ethynylene arrays from boronate ester derivatives using the thienyl group as an example. Furthermore, poly(2,2′-(1-(4-(1,2-di(thiophen-2-yl)vinyl)phenyl)-2-(2,5-dioctylphenyl)ethene-1,2-diyl)dithiophene) showed good field-effect transistor performance with an excellent mobility up to 0.723 cm2 V-1 s-1 and an on-off ratio of 104.
- Yang, Junwei,Chen, Moyun,Ma, Ji,Huang, Wei,Zhu, Haoyun,Huang, Yuli,Wang, Weizhi
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supporting information
p. 10074 - 10078
(2015/10/12)
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- Methionine: A green and efficient promoter for copper-catalyzed Sonogashira cross-coupling reactions
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In the presence of amino acids as environmentally friendly ligands, CuI-catalyzed Sonogashira cross-coupling of various aryl halides with phenylacetylene was conducted to afford the corresponding internal alkynes. l-Methionine was found to be useful for t
- Hajipour, Abdol R.,Mohammadsaleh, Fatemeh
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p. 787 - 792
(2016/01/25)
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- Efficient catalytic Sonogashira reaction catalysed by modified fibre-palladium(II) complex in air
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A hydroxylamine modified polypropylene fibre [Pd(II)-AOFs] was synthesised and used to catalyse the Sonogashira reaction between phenylacetylene and iodobenzene. The results showed that highly efficient catalytic activity can be achieved for the cross-coupling reaction. More importantly, the reaction conditions are moderate and do not require inert gas protection. The catalyst could be readily extracted by simple operations and conveniently recycled four times without an obviously significant decrease in activity.
- Wu, Zhi-Chuan,Sun, Yu-Xing,Xu, Mao-Dong,Tao, Ting-Xian
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p. 478 - 481
(2015/11/03)
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- Copper-free Sonogashira cross-coupling reactions catalyzed by an efficient dimeric C,N-palladacycle in DMF/H2O
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Very small concentrations of a dimeric C,N-palladacycle were used as an efficient homogeneous catalyst for Sonogashira cross-coupling reactions between various aryl halides and phenylacetylene. The catalytic reactions were performed without the need for copper in DMF/H2O. This catalytic system shows excellent yields for aryl iodides and bromides and even in the case of aryl chlorides.
- Karami, Kazem,Haghighat Naeini, Nasrin
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p. 1199 - 1207
(2016/03/01)
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- 3,6-Di(pyridin-2-yl)-1,2,4,5-tetrazine capped Pd(0) nanoparticles: A catalyst for copper-free Sonogashira coupling of aryl halides in aqueous medium
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3,6-Di(pyridin-2-yl)-1,2,4,5-tetrazine (pytz) capped Pd(0) nanoparticles (TzPdNPs) as a catalyst in the Sonogashira coupling of aryl halides in aqueous medium with diminished homocoupling is reported. The methodology provides a facile route to obtain polyfunctional alkynes under ligand- and copper-free conditions. The procedure is also efficient for aryl chlorides.
- Das, Sudipto,Samanta, Suvendu,Ray, Shounak,Biswas, Papu
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p. 75263 - 75267
(2015/09/21)
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- Palladium anchored on amine-functionalized K10 as an efficient, heterogeneous and reusable catalyst for carbonylative Sonogashira reaction
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The present work describes the immobilization of palladium chloride (II) on the amine functionalized K10 support and its application toward the carbonylative Sonogashira reactions. The various catalyst characterization techniques revealed the successful grafting of APTES moiety on the K10 clay surface through covalent bonding and Pd with the NH2 groups of APTES@K10 through co-ordinate bonding. The immobilized catalyst was successively applied for copper and phosphine free carbonylative Sonogashira reaction of aryl and hetero aryl iodides with terminal alkynes. To our delight, the electron withdrawing aryl halides can be efficiently utilized as an electrophiles giving higher selectivity toward carbonylated products. Moreover, dibenzoylmethane which is a potential synthetic intermediate in organic transformation has been also synthesized using this protocol. Recovery of catalyst by simple filtration and its reuse up to four consecutive cycles ensure the robustness of present catalytic protocol.
- Chavan, Sujit P.,Varadwaj, G.Bishwa Bidita,Parida, Kulamani,Bhanage, Bhalchandra M.
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p. 237 - 245
(2015/10/12)
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- Rh-catalyzed decarbonylation of conjugated ynones via carbon-alkyne bond activation: Reaction scope and mechanistic exploration via DFT calculations
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In this full article, detailed development of a catalytic decarbonylation of conjugated monoynones to synthesize disubstituted alkynes is described. The reaction scope and limitation has been thoroughly investigated, and a broad range of functional groups
- Dermenci, Alpay,Whittaker, Rachel E.,Gao, Yang,Cruz, Faben A.,Yu, Zhi-Xiang,Dong, Guangbin
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p. 3201 - 3210
(2015/06/17)
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- Palladium particles from oxime-derived palladacycle supported on Fe3O4/oleic acid as a catalyst for the copper-free Sonogashira cross-coupling reaction
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An oxime-derived palladacycle was synthesized using 4-bromobenzoxime and pyridine in CHCl3, and characterized by FT-IR and 1H NMR spectroscopy. This Pd complex was supported on Fe3O4/oleic acid and shown to be an efficient catalyst for the copper-free Sonogashira cross-coupling reaction of various aryl halides with phenylacetylene in air and in ethanol or mixed aqueous medium. The oxime-derived palladacycle gave highly active palladium nanoparticles for the organic synthesis. The coupling products were obtained in high yields with low Pd loading and the heterogeneous catalyst can be separated by an external magnet and reused six times without loss of its activity. The characterization of the catalyst was carried out by XRD, SEM and TEM. Both TEM and XRD revealed that the palladium nanoparticles were well dispersed with diameters from 5 to 10 nm and average size 9.97 nm.
- Karami, Kazem,Najvani, Samaneh Dehghani,Naeini, Nasrin Haghighat,Hervés, Pablo
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p. 1047 - 1053
(2015/07/01)
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- Synthesis and properties of sulfonated poly(phenylene sulfone)s without ether linkage by Diels-Alder reaction for PEMFC application
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A new sulfonated poly(phenylene sulfone) polymer (SPPS) was synthesized by Diels-Alder polymerization from 1,4-bis(2,4,5-triphenylcyclopentadienone)benzene (BTPCPB) and 4,4′-diethynylphenylsulfone, and followed by sulfonation reaction with chlorosulfuric
- Lim, Youngdon,Lee, Hyunchul,Lee, Soonho,Jang, Hohyoun,Hossain, Md. Awlad,Cho, Younggil,Kim, Taeho,Hong, Youngtaik,Kim, Whangi
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- Palladium-ADC complexes as efficient catalysts in copper-free and room temperature Sonogashira coupling
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The metal-mediated coupling between cis-[PdCl2(CNR 1)2] [R1 = cyclohexyl (Cy) 1, t-Bu 2, 2,6-Me2C6H3 (Xyl) 3, 2-Cl-6-MeC 6H3 4] and hydrazones H2
- Valishina, Elena A.,Silva, M.Fátima C. Guedes Da,Kinzhalov, Mikhail A.,Timofeeva, Svetlana A.,Buslaeva, Tatyana M.,Haukka, Matti,Pombeiro, Armando J.L.,Boyarskiy, Vadim P.,Kukushkin, Vadim Yu.,Luzyanin, Konstantin V.
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p. 162 - 171
(2014/11/07)
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- Copper- and Phosphane-Free Sonogashira Coupling of Arenediazonium o-Benzenedisulfonimides
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Arenediazonium o-benzenedisulfonimides can be used as efficient reagents in Sonogashira coupling reactions. In this work, reactions were carried out in DMSO under very mild conditions (without copper or phosphanes), and gave rise to arylated alkynes in good to excellent yields (25 examples, average yield 83 %). o-Benzenedisulfonimide could be recovered from all the reactions in yields of >80 %, so it could be recycled for the preparation of other diazonium salts. Mechanistic insights revealed the fundamental roles of DMSO and the anion of o-benzenedisulfonimide in the formation of the catalyst, and also the importance of DMSO in the catalytic cycle. The Sonogashira coupling between are diazonium o-benzenedisulfonimides and terminal alkynes is a powerful method for the formation of arylated alkynes. No copper, phosphanes, bases, or co-catalysts are needed. Mechanistic insights highlighted the fundamental roles of DMSO and o-benzenedisulfonimide in the formation of the catalyst, and also the important role of DMSO in the catalytic cycle.
- Barbero, Margherita,Cadamuro, Silvano,Dughera, Stefano
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p. 598 - 605
(2015/10/05)
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- Copper- and phosphane-free sonogashira coupling of arenediazonium o-benzenedisulfonimides
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Arenediazonium o-benzenedisulfonimides can be used as efficient reagents in Sonogashira coupling reactions. In this work, reactions were carried out in DMSO under very mild conditions (without copper or phosphanes), and gave rise to arylated alkynes in good to excellent yields (25 examples, average yield 83 %). o-Benzenedisulfonimide could be recovered from all the reactions in yields of >80 %, so it could be recycled for the preparation of other diazonium salts. Mechanistic insights revealed the fundamental roles of DMSO and the anion of o-benzenedisulfonimide in the formation of the catalyst, and also the importance of DMSO in the catalytic cycle. The Sonogashira coupling between are diazonium o-benzenedisulfonimides and terminal alkynes is a powerful method for the formation of arylated alkynes. No copper, phosphanes, bases, or co-catalysts are needed. Mechanistic insights highlighted the fundamental roles of DMSO and o-benzenedisulfonimide in the formation of the catalyst, and also the important role of DMSO in the catalytic cycle. Copyright
- Barbero, Margherita,Cadamuro, Silvano,Dughera, Stefano
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p. 598 - 605
(2014/02/14)
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- Sonogashira reactions catalyzed by a new and efficient copper(I) catalyst incorporating N-benzyl DABCO chloride
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A new and effective catalytic system using [N-benzyl DABCO] +[Cu4Cl5]- was developed for the palladium-free Sonogashira cross-coupling reactions of phenylacetylene with a variety of aryl halides. In this homogeneous catalytic system, 1-benzyl-4-aza-1-azoniabicyclo[2.2.2]octane chloride, a quaternary ammonium salt containing a coordinating center, plays an important role and increases the efficiency of Cu(I) species during the reaction. A number of internal alkynes were produced in moderate to excellent yields, in short reaction times in DMF at 135 °C.
- Hajipour, Abdol R.,Mohammadsaleh, Fatemeh
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p. 3459 - 3462
(2014/06/10)
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- Sonogashira couplings catalyzed by collaborative (N-heterocyclic carbene)-copper and -palladium complexes
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A general protocol for the Sonogashira reaction using a 100:1 combination of (N-heterocyclic carbene)-Cu and (N-heterocyclic carbene)-Pd complexes is presented. Catalyst loadings of 1 mol % (NHC)-Cu and 0.01 mol % (NHC)-Pd allow for the coupling of aryl bromides and aryl alkynes, in air and in a non-anhydrous solvent, in high yields.
- Gallop, Christopher W. D.,Chen, Ming-Tsz,Navarro, Oscar
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supporting information
p. 3724 - 3727
(2014/08/05)
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- Design, synthesis and structure-activity relationships of some novel, highly potent anti-invasive (E)- and (Z)-stilbenes
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In our ongoing exploration of the structure-activity landscape of anti-invasive chalcones, we have prepared and evaluated a number of structurally related (E)- and (Z)-stilbenes. These molecules exhibited an extraordinary high in vitro potency in the chick heart invasion assay, being active up to 10 nmol L-1, a concentration level a 100-fold lower than the lowest effective doses that have been reported for natural analogues. Furthermore, they possess an interesting pharmacological profile in silico.
- Roman, Bart I.,De Coen, Laurens M.,Mortier, Séverine Thérèse F.C.,De Ryck, Tine,Vanhoecke, Barbara W.A.,Katritzky, Alan R.,Bracke, Marc E.,Stevens, Christian V.
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p. 5054 - 5063
(2013/09/02)
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- Metal-free, acid-promoted synthesis of imidazole derivatives via a multicomponent reaction
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An expedient and metal-free synthetic route has been developed for the construction of tri- and tetrasubstituted imidazole derivatives via acid promoted multicomponent reaction methodology. The reaction proceeded smoothly with a range of functionalities to produce the imidazole scaffolds in good to excellent yields.
- Chen, Chung-Yu,Hu, Wan-Ping,Yan, Pi-Cheng,Senadi, Gopal Chandru,Wang, Jeh-Jeng
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supporting information
p. 6116 - 6119
(2014/01/17)
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- Microwave-promoted copper-free Sonogashira-Hagihara couplings of aryl imidazolylsulfonates in water
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Aryl imidazol-1-ylsulfonates have been efficiently cross-coupled with aryl-, alkyl-, and silylacetylenes in neat water under copper-free conditions at 110 °C assisted by microwave irradiation. Using 0.5mol% of an oxime palladacycle as precatalyst, 2-dicyclohexylphosphino-2′,6′- dimethoxybiphenyl (SPhos, 2mol%) as ligand, hexadecyltrimethylammonium bromide (CTAB) as additive, and triethylamine (TEA) as base, a wide array of disubstituted alkynes has been prepared in good to high yields in only 30min. Copyright
- Civicos, Jose F.,Alonso, Diego A.,Najera, Carmen
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supporting information
p. 203 - 208
(2013/03/14)
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- Decyl(tri- tert -butyl)phosphonium tetrafluoroborate/palladium acetate: An effective catalyst for cross-coupling reaction of arylbromides with phenylacetylene in copper-free conditions
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Abstract The phosphonium salts with sterically hindered cation and noncoordinating anion can be used as phase-transfer reagent in the Sonogashira cross-coupling reaction allowing copper- and amine-free protocol. The reactions proceed under mild conditions
- Ermolaev, Vadim,Miluykov, Vasiliy,Arkhipova, Daria,Zvereva, Elena,Sinyashin, Oleg
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p. 168 - 170
(2013/07/05)
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- Magnetite (Fe3O4) nanoparticles-catalyzed Sonogashira- Hagihara reactions in ethylene glycol under ligand-free conditions
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A novel application of nanoparticles of paramagnetic magnetite (Fe 3O4) as an efficient catalyst for carbon-carbon bond formation via the Sonogashira-Hagihara reaction under heterogeneous ligand-free conditions in ethylene glycol (EG) is described. By using this catalyst, arylalkynes are produced from the reaction of aryl iodides and activated heteroaryl bromides with alkynes. The results are reproducible using the catalyst, which was prepared from different sources. The catalyst is easily separated by an external magnetic field from the reaction mixture. The separated catalyst can be recycled for several consecutive runs without appreciable loss of its catalytic activity.
- Firouzabadi, Habib,Iranpoor, Nasser,Gholinejad, Mohammad,Hoseini, Jafar
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experimental part
p. 125 - 132
(2011/03/22)
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- Highly effective copper-catalyzed decarboxylative coupling of aryl halides with alkynyl carboxylic acids
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We have developed a highly effective copper-catalyzed decarboxylative coupling of alkynylcarboxylic acids with various aryl and alkyl halides at 2 mol% loading of copper. This method is simple, economical and practical for the synthesis of disubstituted alkyne compounds.
- Qu, Xiaoming,Li, Tingyi,Sun, Peng,Zhu, Yan,Yang, Hailong,Mao, Jincheng
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supporting information; experimental part
p. 6938 - 6942
(2011/10/31)
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- Pd-catalyzed domino synthesis of internal alkynes using triarylbismuths as multicoupling organometallic nucleophiles
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Figure presented The domino coupling reaction of 1,1-dibromo-1-alkenes with triarylbismuth nucleophiles has been demonstrated to furnish disubstituted alkynes directly under catalytic palladium conditions. The couplings of triarylbismuths as multicoupling nucleophiles with 3 equiv of 1,1-dibromo-1-alkenes are very fast, affording high yields of alkynes in a short reaction time. Thus, an efficient domino process has been accomplished using 1,1-dibromo-1-alkenes as surrogates for internal alkyne synthesis in couplings with triarylbismuths in a one-pot operation.
- Rao, Maddali L. N.,Jadhav, Deepak N.,Dasgupta, Priyabrata
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supporting information; experimental part
p. 2048 - 2051
(2010/07/03)
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- Fast copper-, ligand- and solvent-free Sonogashira coupling in a ball mill
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A solvent-free method for the Sonogashira coupling reaction was established under ball milling conditions without the use of copper or additional ligands. Pd(OAc)2 or Pd(PPh3)4 in combination with 1,4-diazabicyclo[2.2.2]octane (DABCO) were chosen as catalysts and base, respectively. The reaction was investigated using a variety of aryl halides and acetylenes and with different amounts of the Pd-catalyst and DABCO. Results indicated that the employment of Pd(OAc)2 in combination with SiO2 as a grinding auxiliary preferentially induces the transformation of aryl iodides to the corresponding Sonogashira coupling products. In contrast, both the substitution of SiO2 by Al 2O3 or replacement of Pd(OAc)2 with Pd(PPh 3)4 enable the reaction of aryl bromides with phenylacetylenes. The selective reaction of bis-ethynyl compounds to double-coupled products and the influence of further common bases on the reaction was also scrutinized, confirming the high reactivity of DABCO as a base for solvent-free transformations.
- Thorwirth, Rico,Stolle, Achim,Ondruschka, Bernd
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supporting information; experimental part
p. 985 - 991
(2010/07/14)
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- Solvent-free Sonogashira coupling reaction via high speed ball milling
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Herein, we report on the solvent-free Sonogashira reaction utilizing high speed ball milling. Sonogashira coupling of a variety of para substituted aryl halides were performed with trimethylsilylacetylene or phenylacetylene. We observed that iodo and bromo substituted aromatics successfully undergo Sonogashira coupling. However, chloro and fluoro substituted aryl compounds were unreactive. Conducting the coupling reaction in the absence of copper iodide led to low yields. Alternately, if the reaction is conducted with a copper ball in a copper vial in lieu of copper iodide, the coupling product is observed in high yields. This demonstrates the first report on the use of the vial and ball material as a catalyst in a ball milled chemical reaction. The Royal Society of Chemistry 2009.
- Fulmer, Dennis A.,Shearouse, William C.,Medonza, Shareika T.,MacK, James
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experimental part
p. 1821 - 1825
(2011/02/24)
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- Palladhim-catalyzed decarboxylative sp-sp2 cross-coupling reactions of aryl and vinyl halides and triflates with α,β-ynoic acids using silver oxide
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Palladium-catalyzed decarboxylative sp-sp2 cross-coupling reactions of aryl and vinyl halides and triflates with α,β-ynoic acids using silver oxide have been developed. A variety of α,β-ynoic acids were readily decarboxylated in the presence of
- Kim, Hyunseok,Lee, Phil Ho
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supporting information; scheme or table
p. 2827 - 2832
(2010/03/26)
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- Copper- and base-free Sonogashira-type cross-coupling reaction of triarylantimony dicarboxylates with terminal alkynes under an aerobic condition
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A simple copper- and base-free palladium-catalyzed Sonogashira-type cross-coupling by the use of triarylantimony dicarboxylates is described. Reaction of triarylantimony diacetates with terminal alkynes in the presence of 1 mol % of PdCl2(PPhs
- Wang, Xuan,Qin, Weiwei,Kakusawa, Naoki,Yasuike, Shuji,Kurita, Jyoji
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body text
p. 6293 - 6297
(2010/01/18)
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- Sonogashira cross-coupling reactions and construction of the indole ring system using a robust, silica-supported palladium catalyst
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The use of a recyclable silica-supported palladium catalyst in Sonogashira couplings and indole syntheses using a range of functionalised substrates is described. The catalyst is shown to be both robust and versatile, effecting the synthesis of 2-phenylindole in quantitative yield without the need for N-protection, a copper co-catalyst, a base, or a solvent. Georg Thieme Verlag Stuttgart.
- Tyrrell, Elizabeth,Whiteman, Leon,Williams, Neil
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experimental part
p. 829 - 835
(2009/07/25)
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- Zinc chloride-promoted aryl bromide-alkyne cross-coupling reactions at room temperature
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(Chemical Equation Presented) Substoichiometric amounts of ZnCl2 promote the room temperature, Pd/P(t-Bu)3-catalyzed cross-coupling of aryl bromides with alkynes. Pd(I) dimer 1 is demonstrated to be a particularly active precatalyst for this reaction. The reaction is general for a wide variety of aryl bromides.
- Finke, Aaron D.,Elleby, Eric C.,Boyd, Michael J.,Weissman, Haim,Moore, Jeffrey S.
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supporting information; experimental part
p. 8897 - 8900
(2010/03/01)
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- Palladium-catalyzed copper-free sonogashira coupling reaction in water and acetone
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An efficient palladium-catalyzed copper-free Sonogashira reaction in water and acetone has been developed under mild conditions. The results showed that the aryl iodides could carry out the cross-coupling reaction with a variety of terminal alkynes in high yields in water-acetone in the absence of amine, copper(I) salts, or phosphine ligands at 60°C for one hour, and good yields were obtained for aryl bromides at 60°C for 12-24 hours in the presence of triphenylphosphine and piperidine. The method could be used to synthesize polyethynyl aromatic compounds in a one-pot reaction. Georg Thieme Verlag Stuttgart.
- Shi, Shengyin,Zhang, Yuhong
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p. 1843 - 1850
(2008/02/10)
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- New fluorophores with rod-shaped polycyano π-conjugated structures: Synthesis and photophysical properties
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Novel rod-shaped polycyano-oligo(phenyleneethynylene)s were synthesized by Pd cross-coupling reaction. Polycyano groups were found to greatly improve the emission efficiency (Φf) of OPEs. By the end donor modification, we achieved the creation of very intense blue light-emitting fluorophore with the SMe group (Φf) = 0.972, log ε 4.89, λ em 455 nm) and very intense yellow light-emitting fluorophore with the NMe2 group (Φf = 0.999, log ε 4.75, λem 555 nm). Contrasting Φf solvent dependency of 6 and 7 and a linear relationship between Φf and σp-X over the whole region of σp-X were also found.
- Yamaguchi, Yoshihiro,Ochi, Takanori,Wakamiya, Tateaki,Matsubara, Yoshio,Yoshida, Zen-Ichi
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p. 717 - 720
(2007/10/03)
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- New synthetic applications of indium organometallics in cross-coupling reactions
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The use of indium organometallics in multifold and sequential cross-coupling reactions is reported. Triorganoindium reagents (R3In) react, under palladium catalysis, with oligohaloarenes affording the multiple cross-coupling products in a single operation. In the reaction, the three organic groups (alkyl, aryl, alkenyl or alkynyl) attached to indium are efficiently transferred to the electrophile, with only a slight excess of organometallic reagent. We demonstrate that indium organometallics are useful reagents for sequential cross-coupling reactions. This reaction illustrates the high chemoselectivity of R3In. Georg Thieme Verlag Stuttgart.
- Pena, Miguel A.,Perez Sestelo, Jose,Sarandeses, Luis A.
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p. 485 - 492
(2007/10/03)
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