- Synthesis and structural characterization of palladium(II) 2-(arylazo)naphtholate complexes and their catalytic activity in Suzuki and Sonogashira coupling reactions
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A family of five palladium(II) 2-(arylazo)naphtholate complexes, [PdCl(PPh3)(L)] (L = O, N-donor of bidentate 2-(arylazo)naphtholate ligands), have been synthesized and characterized by elemental analysis and spectral (FT-IR, UV–Vis, 1H-NMR and 13C-NMR) methods. Further, the catalytic efficiency of all the complexes have been investigated for Suzuki and Sonogashira coupling reaction of various aryl halides.
- Munusamy, Sathya,Muniyappan, Premkumar,Galmari, Venkatachalam
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- Highly stable magnetically separable copper nanocatalyst as an efficient catalyst for C(sp2)–C(sp) and C(sp2)–C(sp2) cross-coupling reactions
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A copper catalyst has been explored as an efficient and recyclable catalyst to effect Sonogashira and Suzuki cross-coupling reactions. After modification of 2-(((piperazin-1-ylmethyl)imino)methyl)phenol (PP) on the surface of amorphous silica-coated iron oxide (Fe3O4@SiO2@Cl) magnetic core–shell nanocomposite, copper(II) chloride was employed to synthesize the Fe3O4@SiO2@PP-Cu catalyst, affording a copper loading of 1.52?mmol?g?1. High yield, low reaction times, non-toxicity and recyclability of the catalyst are the main merits of this protocol. The catalyst was characterized using Fourier transform infrared, X-ray photoelectron, energy-dispersive X-ray and inductively coupled plasma optical emission spectroscopies, X-ray diffraction, scanning and transmission electron microscopies, and vibrating sample magnetometry.
- Keypour, Hassan,Balali, Masomeh,Nejat, Razieh,Bagherzadeh, Mojtaba
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- Atom-Economical Thiocyanation-Amination of Alkynes with N-Thiocyanato-Dibenzenesulfonimide
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A highly regioselective protocol for intermolecular thiocyanation-amination of alkynes by N-thiocyano-dibenzenesulfonimide (NTSI) as the SCN and nitrogen sources has been developed. A C-S bond and C-N bond are simultaneously constructed in only one step. The reaction under simple mild conditions features a broad substrate scope, atom economy, high yields (up to 94%), and excellent functional group tolerance.
- Wu, Haopeng,Shao, Chukai,Wu, Di,Jiang, Liang,Yin, Hongquan,Chen, Fu-Xue
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p. 5327 - 5335
(2021/04/06)
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- Reductive Aromatization of Quinols with B2pin2 as Deoxidizing Agent
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We have demonstrated B2pin2 as superior deoxidizing agent for the reductive deoxygenation of quinol derivatives under basic conditions. A wide range of highly functionalized phenols were obtained in good yields including a complex drug molecule, which revealed the high functional group tolerance of this protocol.
- Liu, Bin,Xu, Yin,Luo, Zhibin,Xie, Jimin
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p. 1022 - 1024
(2020/03/19)
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- Palladium(II) complexes containing sterically bulky O, N donor ligands: Synthesis, characterization and catalytic activity in the Suzuki-Miyaura and Sonogashira coupling reactions
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A new class of palladium(II)1-(arylazo)naphtholate complexes of the type [Pd(L1-4)2] containing sterically bulky O, N donor functionalized arylazo ligands has been synthesized. These palladium(II) complexes were characterized by elemental analysis and spectral (FT-IR, UV–Vis, 1H NMR and 13C NMR) studies. The molecular structure of the Palladium(II) complexes [Pd(L1)2] and [Pd(L2)2] were established by X-ray crystallography. These complexes were found to efficiently catalyze the Suzuki-Miyaura coupling of arylboronic acids and aryl halides, and the Sonogashira reaction of aryl halides and phenylacetylene in DMF and i-PrOH media to afford the corresponding C–C coupling products in high yields.
- Nandhini, Raja,Vijayan, Paranthaman,Venkatachalam, Galmari
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- A Simple Nickel Catalyst Enabling an E-Selective Alkyne Semihydrogenation
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Stereoselective alkyne semihydrogenations are attractive approaches to alkenes, which are key building blocks for synthesis. With regards to the most atom-economic reducing agent dihydrogen (H2), only few catalysts for the challenging E-selective alkyne semihydrogenation have been disclosed, each with a unique substrate scope profile. Here, we show that a commercially available nickel catalyst facilitates the E-selective alkyne semihydrogenation of a wide variety of substituted internal alkynes. This results in a simple and broadly applicable overall protocol to stereoselectively access E-alkenes employing H2, which could serve as a general method for synthesis.
- Thiel, Niklas O.,Kaewmee, Benyapa,Tran Ngoc, Trung,Teichert, Johannes F.
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supporting information
p. 1597 - 1603
(2020/02/05)
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- Sustainable Ligand-Free Heterogeneous Palladium-Catalyzed Sonogashira Cross-Coupling Reaction in Deep Eutectic Solvents
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The commercially available and cheap Pd/C was found to promote Sonogashira couplings in the environmentally friendly choline chloride/glycerol eutectic mixture in the absence of external ligands. Under heterogeneous conditions, (hetero)aryl iodides were successfully coupled with both aromatic and aliphatic alkynes in yields ranging from 50 to 99 % within 3 h at 60 °C. The aforementioned catalytic system proved to be effective also towards electron-rich iodides, which are notoriously known to be poorly reactive in Pd-catalyzed Sonogashira coupling reactions. The eutectic mixture and the catalyst could easily and successfully be recycled up to four times with an E-factor as low as 24.4.
- Messa, Francesco,Dilauro, Giuseppe,Perna, Filippo M.,Vitale, Paola,Capriati, Vito,Salomone, Antonio
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p. 1979 - 1984
(2020/02/20)
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- Cobalt catalyzed stereodivergent semi-hydrogenation of alkynes using H2O as the hydrogen source
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Cobalt-catalyzed stereodivergent semi-hydrogenation of internal alkynes to alkenes is developed. The reaction proceeded through transfer hydrogenation under mild conditions using a base metal CoI2 as the catalyst, and H2O/MeOH as the hydrogen source with Zn as the reductant. The E/Z-selectivity of the product could be switched by changing the solvent and by inclusion/exclusion of a bidentate phosphine ligand (dppe). This method provides a simple and cost effective pathway for the synthesis of 1,2-dideuterioalkenes.
- Li, Kangkui,Khan, Ruhima,Zhang, Xuexin,Gao, Yang,Zhou, Yongyun,Tan, Heng,Chen, Jingchao,Fan, Baomin
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supporting information
p. 5663 - 5666
(2019/05/21)
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- Sonogashira Couplings Catalyzed by Fe Nanoparticles Containing ppm Levels of Reusable Pd, under Mild Aqueous Micellar Conditions
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Nanoparticles derived from FeCl3 containing the ligand XPhos and only 500 ppm Pd effect Sonogashira couplings in water between rt and 45 °C. The entire aqueous reaction medium can be easily recycled using an "in-flask" extraction. Several tande
- Handa, Sachin,Jin, Bo,Bora, Pranjal P.,Wang, Ye,Zhang, Xiaohua,Gallou, Fabrice,Reilly, John,Lipshutz, Bruce H.
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p. 2423 - 2431
(2019/03/08)
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- Ligand-free, recyclable palladium-functionalized magnetite nanoparticles as a catalyst in the Suzuki-, Sonogashira, and Stille reaction
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A magnetically reusable ligand-free Fe3O4 palladium functionalized catalyst system was successfully prepared without the use of reducing agents, but by making use of the reduction potential of magnetite. The stabilizer was variated depending on the investigated reaction, whereby poly(ethylene glycol) (PEG) stabilized nanoparticles were used for the Suzuki reaction, as it requires protic conditions, while oleic acid stabilized nanoparticles were used for the Sonogashira and Stille reaction. It was found that it was possible to perform the Suzuki reaction and the Sonogashira reaction resulting in good to excellent conversions under air. Despite the good results for the Suzuki and the Sonogashira reaction it was not possible to perform the Stille reaction using this easily synthesized catalyst system due to the poisoning of the reusable catalyst by the tin-compound. Furthermore, the reusable catalyst system was recycled and reused for five times, resulting in a separable, straightforward and less time-consuming catalyst system.
- De Cattelle, Amaury,Billen, Arne,O'Rourke, Galahad,Brullot, Ward,Verbiest, Thierry,Koeckelberghs, Guy
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- Magnetically retrievable N-heterocyclic carbene-silver complex with wingtip ferrocenyl group for Sonogashira coupling
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A new magnetically retrievable N-heterocyclic carbene-silver complex with wingtip ferrocenyl group has been prepared by multi-step procedure. The formation of complex was confirmed on the basis of analytical techniques such as FT-IR, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), X-Ray diffraction (XRD), transmission electron microscopy (TEM) and VSM (vibrating sample magnetometer) analysis. The complex was successfully employed as an efficient heterogeneous catalyst for Sonogashira coupling reaction of aryl halides with terminal alkynes. The complex could be separated easily by applying external magnet. The reusability studies revealed that complex can be reused up to eight times without significant decrease in catalytic activity.
- Naikwade, Altafhusen,Bansode, Prakash,Rashinkar, Gajanan
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p. 112 - 122
(2018/05/03)
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- Palladium nanoparticles immobilized on EDTA-modified Fe3O4@SiO2 nanospheres as an efficient and magnetically separable catalyst for Suzuki and Sonogashira cross-coupling reactions
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In this study, a novel heterogeneous palladium catalyst was synthesized by anchoring palladium onto ethylenediaminetetraacetic acid (EDTA)-coated Fe3O4@SiO2 magnetic nanocomposite and used for the Suzuki and Sonogashira cross-coupling reactions. The properties of the magnetic catalyst were characterized by FT-IR, XRD, TEM, FE-SEM, DLS EDX, XPS, N2 adsorption-desorption isotherm analysis, TGA, VSM, elemental analysis and the loading level of Pd in catalyst was measured to be 0.51?mmol/g by ICP. The catalyst was used in Suzuki cross-coupling reactions of various aryl halides, including less reactive chlorobenzenes with phenylboronic acid without any additive or ligand under green conditions. Furthermore, we have reported this recyclable catalytic system for Sonogashira cross-coupling reactions of various aryl halides (I, Br, Cl) under copper and ligand-free conditions in the presence of DMF/H2O (1:2/v:v) as a solvent. The magnetic catalyst could also be separated by an external magnet and reused six times without any significant loss of activity.
- Esmaeilpour, Mohsen,Zahmatkesh, Saeed,Fahimi, Nafiseh,Nosratabadi, Mehran
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- Palladium nanoparticles immobilized on cyclodextrin-decorated halloysite nanotubes: Efficient heterogeneous catalyst for promoting copper- and ligand-free Sonogashira reaction in water–ethanol mixture
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Combining the excellent features of halloysite nanoclay and cyclodextrin, a novel hybrid system was designed and synthesized based on covalent attachment of tosylated cyclodextrin to thiosemicarbazide-functionalized halloysite nanoclay and used for the im
- Sadjadi, Samahe
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- Transition-Metal-Free Highly Chemoselective and Stereoselective Reduction with Se/DMF/H2O System
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A novel metal-free reduction system, in which H2Se (or HSe-) produced in situ from Se/DMF/H2O acts as the active reducing species, has been developed. By using water as an inexpensive, safe, and environmentally friendly surrogate as the hydrogen donor, this new reduction system incorporating Se/DMF/H2O displayed high selectivity and good activity in the reduction of α,β-unsaturated ketones and alkynes. Therefore, this reduction system has great potential to be a general and practical reduction methodology in organic transformation.
- Li, Hong-Chen,An, Cui,Wu, Ge,Li, Guo-Xing,Huang, Xiao-Bo,Gao, Wen-Xia,Ding, Jin-Chang,Zhou, Yun-Bing,Liu, Miao-Chang,Wu, Hua-Yue
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supporting information
p. 5573 - 5577
(2018/09/12)
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- N-heterocyclic carbene-Pd(II) complex based on theophylline supported on Fe3O4@SiO2 nanoparticles: Highly active, durable and magnetically separable catalyst for green Suzuki-Miyaura and Sonogashira-Hagihara coupling reactions
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In this paper, a novel heterogeneous palladium catalyst was synthesized by anchoring N-heterocyclic carbene-Pd(II) complex based on theophylline on magnetic Fe3O4@SiO2 nanoparticles. The synthesized magnetic composite was characterized by fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray analysis (EDX), thermogravimetric analysis (TGA), vibration sample magnetometry (VSM), transmission electron microscopy (TEM), field emission scanning electron microscopy (FE-SEM), dynamic light scattering (DLS), N2 adsorption-desorption isotherm analysis (BET), UV–vis spectroscopy and elemental analysis. Also, loading content of palladium on the catalyst was measured by inductive coupled plasma (ICP) analysis. The synthesized catalyst was used successfully for the Suzuki cross-coupling reactions of various aryl halides (I, Br, Cl) with phenylboronic acids. This reaction was best performed in water as a green solvent in the presence of just 0.37–0.5 mol% of the catalyst at 60 °C. Also, we have reported this recyclable catalytic system as a stable phosphine-free Pd catalyst for the Sonogashira cross-coupling of aryl halides (I, Br, Cl) with terminal aromatic and aliphatic alkynes under solvent-free conditions. All coupling reactions proceeded with good to excellent yields. The catalyst showed good stability and was recovered and reused for eight reaction cycles without a significant loss in its catalytic activity. Also, the leaching of the catalyst has been examined by a hot filtration test and ICP-AES analysis.
- Esmaeilpour, Mohsen,Sardarian, Ali Reza,Firouzabadi, Habib
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- Heterogenized Cu (II) salen complex grafted on graphene oxide nanosheets as a precursing catalyst for the Pd-free Sonogashira coupling
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Cu (II) salen complex immobilized on graphene oxide nanosheets [Cu (II) salen@GO] was synthesized with 3-chloropropyltrimethoxysilan as a linker and wholly characterized using various techniques like X-ray diffraction, Fourier-transform infrared, scanning electron microscopy/energy-dispersive X-ray spectroscopy, transmission electron microscopy, as well as atomic absorption spectroscopy (AAS). Cu (II) salen@GO as an effective heterogeneous catalyst has been investigated for the Sonogashira coupling reaction in dimethylsulfoxide with good to high yield (98%) in 4?hr at 110°C when the loading of Cu was 0.7?mmol?g?1 based on Cu element analysis by AAS. It was understood that heterogeneous catalyst was as active as its homogeneous analog, and presented good recoverability and no significant loss in activity within successive runs.
- Ghabdian, Mahdieh,Nasseri, Mohammad A.,Allahresani, Ali,Motavallizadehkakhky, Alireza
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- Sustainable HandaPhos-ppm Palladium Technology for Copper-Free Sonogashira Couplings in Water under Mild Conditions
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Complexation of ca. 1000 ppm Pd(OAc)2 with the ligand HandaPhos (1-1.5:1) leads to a precatalyst that efficiently mediates Sonogashira couplings in aqueous nanomicelles under very mild conditions. Neither copper nor organic solvent is required
- Handa, Sachin,Smith, Justin D.,Zhang, Yitao,Takale, Balaram S.,Gallou, Fabrice,Lipshutz, Bruce H.
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supporting information
p. 542 - 545
(2018/02/10)
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- Recyclable and eco-friendly Pd-complexed graphene oxide/N-heterocyclic carbene catalyst for various coupling reactions in aqueous phase
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In this study, we report recyclable Pd-complexed graphene oxide (GO) catalysts with a bulky N-heterocyclic carbene (NHC) ligand (GO/NHC-Pd) for various cross-coupling reactions in the aqueous phase. To prepare GO/NHC-Pd, the NHC precursor and a trimethoxy-silane linker were combined on the GO surface via condensation, followed by the Pd chelation over GO/NHC. The GO-based catalysts were applied to three types of C–C cross-coupling reactions including Suzuki, Heck and Sonogashira reactions in the aqueous phase, to evaluate their catalytic performance. The reusability of the catalysts was tested by performing five consequent cross-coupling reactions.
- Kim, Seongsoo,Cho, Hong-Jun,Shin, Dong-Sik,Lee, Sang-Myung
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supporting information
p. 2421 - 2425
(2017/05/31)
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- Visible-light-enhanced photocatalytic Sonogashira reaction over silicon carbide supported Pd nanoparticles
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Sonogashira reaction of aryl halides with terminal alkynes can be realized by a visible-light-driven heterogeneous catalytic route using silicon carbide supported Pd nanoparticles as the catalyst under copper-, and ligand-free conditions. Under the irradi
- Wang, Bing,Guo, Xiaoning,Jin, Guoqiang,Guo, Xiangyun
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- Reduced graphene oxide supported Cu2O nanoparticles as an efficient catalyst for Sonogashira coupling reaction
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Reduced graphene oxide supported Cu2O nanoparticles were prepared by a liquid-phase reduction method and employed as an efficient heterogeneous catalyst for Sonogashira cross-coupling reaction. The catalyst exhibits high activity and selectivit
- Wang, Bing,Wang, Yingyong,Guo, Xiaoning,Jiao, Zhifeng,Jin, Guoqiang,Guo, Xiangyun
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- Decarboxylative/Sonogashira-type cross-coupling using PdCl2(Cy?Phine)2
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The PdCl2(Cy?Phine)2 precatalyst containing the meta-terarylphosphine ligand, Cy?Phine, can effectively mediate decarboxylative cross-coupling with a diverse range of (hetero-)aryl, aryl and alkyl chlorides including those with unprotected functionality. Using a facile and robust protocol, this process was extended to the first synthesis of symmetrical di(heteroaryl)alkynes via tandem Sonogashira/decarboxylative cross-coupling of heteroaryl chlorides and propiolic acid.
- Yang, Yong,Lim, Yee Hwee,Robins, Edward G.,Johannes, Charles W.
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p. 72810 - 72814
(2016/08/09)
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- Regioselective one-pot synthesis of 2,3-diaryl-2H-1-benzopyrans via Br?nsted acid-catalyzed [4+2] cycloaddition of salicylaldehydes with diarylacetylenes
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A regioselective one-pot synthesis of 2,3-diaryl-2H-1-benzopyrans from easily available various diarylacetylenes and salicylaldehydes via Br?nsted acid-catalyzed [4+2] cycloaddition has been developed. High regioselectivity was observed in the reaction to afford 2-(electron-rich aryl)-3-(electron-poor aryl)-2H-1-benzopyrans in good yields. The present reaction provides versatile access to functionalized 2,3-diaryl-2H-1-benzopyrans, which would be useful as key intermediates for the synthesis of biologically and photochemically active molecules.
- Tanaka, Kenta,Shigematsu, Yosuke,Sukekawa, Mayumi,Hoshino, Yujiro,Honda, Kiyoshi
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supporting information
p. 5914 - 5918
(2016/12/09)
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- Dendrimer-encapsulated Pd(0) nanoparticles immobilized on nanosilica as a highly active and recyclable catalyst for the copper- and phosphine-free Sonogashira-Hagihara coupling reactions in water
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This study demonstrates a new synthetic strategy for the preparation of porous SiO2 for catalytic applications using natural and waste materials from rice husks as the source of biosilica. Biogenic porous silica nanoparticles with a mean diameter of 45 nm were successfully prepared from rice husk (RH) biomass via a new multistep method. During the first step, sodium silicate is extracted from rice husks. Then, cetyltrimethylammonium bromide (CTAB), HCl, and HOAc were added into sodium silicate solution, and the resulting mixture was sonicated. After the hydrothermal reaction, the collected samples were calcinated to obtain silica nanoparticles. Then, dendrimer-encapsulated Pd(0) nanoparticles supported on nano-silica with surface amino groups were fabricated. These materials are prepared by sequestering palladium ions within dendrimers followed by chemical reduction to yield the corresponding zero-valent palladium nanoparticles. The synthesized nanostructures were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA), dynamic light scattering (DLS), N2 adsorption-desorption isotherm analysis, UV-vis spectroscopy and elemental analysis. The morphologies of the catalyst were characterized using a field emission scanning electron microscope (FE-SEM) and a transmission electron microscope (TEM). Also, its Pd content was determined by using an inductively coupled plasma (ICP) analyzer. This catalytic system was used as an efficient catalyst for Sonogashira reaction of aryl halides with alkynes under copper and phosphine ligand-free conditions in water. The catalyst was regenerated for five cycles of reaction without any significant loss in its activity. Also, the analysis of the reaction mixture by the ICP technique showed that the leaching of the catalyst was negligible.
- Esmaeilpour, Mohsen,Sardarian, Alireza,Javidi, Jaber
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p. 4005 - 4019
(2016/06/13)
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- Square-planar Ni(II) thiosemicarbazonato complex as an easily accessible and convenient catalyst for Sonogashira cross-coupling reaction
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A simple route for the synthesis of a new square-planar nickel(II) complex bearing 2-((3-methylthiophen-2-yl)methylene)-N-phenylhydrazinecarbothioamide ligand has been described. The composition of the complex has been established by elemental analysis, F
- Prabhu, Rupesh Narayana,Ramesh, Rengan
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supporting information
p. 4893 - 4897
(2016/10/21)
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- Supramolecular ensemble of a TICT-AIEE active pyrazine derivative and CuO NPs: A potential photocatalytic system for sonogashira couplings
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The donor-acceptor system 4 having pyrazine scaffold as an acceptor moiety coupled to donor amino groups through rotatable phenyl rings has been synthesized, which formed aggregates in aqueous media, exhibited copper induced restriction to intramolecular rotation, and served as a "not quenched" probe for the detection of copper(II) ions. During this process, the aggregates of derivative 4 acted as reactors and stabilizers for the generation of CuO NPs and themselves became oxidized to form polyamine derivative 6. Interestingly, the oxidized species 6 in combination with copper oxide nanoparticles served as light-harvesting antennas and exhibited excellent photocatalytic efficiency in Sonogashira coupling under mild and eco-friendly conditions (room temperature, aqueous media, aerial conditions, and visible light irradiation).
- Deol, Harnimarta,Pramanik, Subhamay,Kumar, Manoj,Khan, Imran A.,Bhalla, Vandana
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p. 3771 - 3783
(2016/07/06)
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- Scope and limitations of a DMF bio-alternative within Sonogashira cross-coupling and Cacchi-type annulation
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Pd-catalysed C-C bond formation is an essential tool within the pharmaceutical and agrochemical industries. Many of these reactions rely heavily on polar aprotic solvents; however, despite their utility, these solvents are incompatible with the drive towards more sustainable chemical synthesis. Herein, we describe the scope and limitations of an alternative to DMF derived from renewable sources (Cyrene) in Sonogashira cross-coupling and Cacchi-type annulations.
- Wilson, Kirsty L.,Kennedy, Alan R.,Murray, Jane,Greatrex, Ben,Jamieson, Craig,Watson, Allan J. B.
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supporting information
p. 2005 - 2011
(2016/10/05)
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- An efficient mesoporous carbon nitride (g-C3N4) functionalized Pd catalyst for carbon-carbon bond formation reactions
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Metal nanoparticles in pristine form without any stabilizing agents and free from agglomeration are very critical for their function and diverse catalytic applications. With the goal to accomplish a molecularly defined Pd-based heterogeneous C-C bond form
- Elavarasan,Baskar,Senthil,Bhanja, Piyali,Bhaumik,Selvam,Sasidharan
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p. 49376 - 49386
(2016/06/15)
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- Sonogashira coupling catalyzed by the Cu(Xantphos)I–Pd(OAc)2system
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An efficient Pd(OAc)2/Cu(Xantphos)I system for Sonogashira coupling is disclosed. Aryl bromides/iodides and electron-poor aryl chlorides were suitable for this reaction. The experimental results suggest that Cu(Xantphos)I plays a unique role in which the phosphine ligand coordinates with copper.
- Liu, Meilin,Ye, Mingyan,Xue, Yeye,Yin, Guodong,Wang, Dunjia,Huang, Jinkun
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supporting information
p. 3137 - 3139
(2016/07/06)
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- Gold-Catalyzed Synthesis of Tropone and Its Analogues via Oxidative Ring Expansion of Alkynyl Quinols
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A new and convenient strategy for the synthesis of functionalized tropone derivatives based on the gold-catalyzed oxidative ring expansion of alkynyl quinols has been developed. The reaction proceeds via gold-catalyzed highly regioselective oxidation foll
- Zhao, Jidong,Liu, Jun,Xie, Xin,Li, Shi,Liu, Yuanhong
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supporting information
p. 5926 - 5929
(2015/12/11)
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- Copper-free Sonogashira reactions catalyzed by a palladium(II) complex bearing pyrenealdehyde thiosemicarbazonate under ambient conditions
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Convenient synthesis of a new square-planar mononuclear palladium(II) complex bearing N,S-donor 1-pyrenaldehyde 4-methyl-3-thiosemicarbazonate (L-) as ligand is described. The identity of the complex has been established as [Pd(L)Cl(PPh3/
- Prabhu, Rupesh Narayana,Pal, Samudranil
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supporting information
p. 5252 - 5256
(2015/08/19)
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- Synthesis and optical properties of cationic cyclopentadienyl iron complexes with diphenylacetylene chromophores
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Cationic cyclopentadienyl iron complexes of arenes are applied in photopolymerization and photocatalysis because of their good photophysical and photochemical properties. In this study, a series of cationic cyclopentadienyl iron complexes with diphenylace
- Shi, Yizhong,Li, Guanglei,Zhao, Baodong,Chen, Yu,Chao, Pengjie,Zhang, Huiqing,Wang, Xiaoning,Wang, Tao
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p. 259 - 265
(2015/02/05)
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- Efficient Sonogashira and Suzuki-Miyaura coupling reaction catalyzed by Pd-Nanoparticles
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The Pd nano particles were electrochemically deposited on nafion-graphene. They showed excellent catalytic activity towards Sonogashira and Suzuki-Miyaura cross-coupling reaction. Benzenediazonium salts were used as alternative to aromatic halide. The developed protocol offers recyclability, easy workups with short reaction time and good-to-excellent product yield. [Figure not available: see fulltext.]
- Balsane, Kishor E.,Shendage, Suresh S.,Nagarkar, Jayashree M.
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p. 425 - 431
(2015/05/13)
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- Synthesis of new surfactant-like triazine-functionalized ligands for Pd-catalyzed Heck and Sonogashira reactions in water
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In this study, a novel class of ligands for palladium-catalyzed C-C coupling reactions in water is introduced. A range of triazine-functionalized ligands were synthesized using 2,4,6-trichloro-1,3,5-triazine (TCT) reagent. Among them, N2,N4,N6-tridodecyl-1,3,5-triazine-2,4,6-triamine (TDTAT) was found to be an efficient ligand for the Pd-catalyzed Heck and Sonogashira reactions in water, which acted as a green solvent. TEM analysis showed that in the presence of TDTAT in water at 80°C, PdCl2 is converted to nanoparticles with an average size of ~3 nm. The formed Pd-nanoparticles act as efficient catalytic species for C-C bond formation reactions in neat water. Under these conditions, Pd-catalyzed Heck and Sonogashira reactions are accomplished without the need for phosphine ligand. The generation of emulsion droplets (5-10 μm) containing Pd(0) nanoparticles would function as an effective reactor to accelerate the rate of the reaction in water media.
- Iranpoor, Nasser,Rahimi, Sajjad,Panahi, Farhad
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p. 49559 - 49567
(2015/06/16)
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- Ligand Control of E/Z Selectivity in Nickel-Catalyzed Transfer Hydrogenative Alkyne Semireduction
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A nickel-catalyzed transfer hydrogenative alkyne semireduction protocol that can be applied to both internal and terminal alkynes using formic acid and Zn as the terminal reductants has been developed. In the case of internal alkynes, the (E)- or (Z)-olefin isomer can be accessed selectively under the same reaction conditions by judicious inclusion of a triphos ligand.
- Richmond, Edward,Moran, Joseph
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p. 6922 - 6929
(2015/10/05)
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- A green approach for copper-free sonogashira reaction of aryl halides with phenylacetylene in the presence of Nano-Pd/Phosphorylated Silica (SDPP/Pd0)
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Silicadiphenyl phosphinite (SDPP) is used as the solid support for the generation of nano SDPP/Pd(0) from PdII as pre-catalyst. This nano catalyst was used for the efficient copper-free Sonogashira reaction of aryl halides in PEG-200 as a solvent. The nan
- Iranpoor, Nasser,Firouzabadi, Habib,Motevalli, Somayeh,Rajabi, Khashayar
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p. 926 - 930
(2015/06/25)
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- Diphenylphosphorylated PEG (DPPPEG) as a new support for generation of nano-Pd(0) as catalyst for carbon-carbon bond formation via copper-free Sonogashira and homocoupling reactions of aryl halides in PEG
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In this study, synthesis and application of diphenylphosphorylated PEG200 (DPPPEG200) are described. Herein, we report a very simple procedure for the preparation of DPPPEG200 as a stable solid through the reaction of PEG200 with ClPPh2. This compound was used as a very suitable ligand for the in situ generation of nano-Pd(0) particles through its reaction with PdCl2 as a pre-catalyst. Isolation of this catalyst is very simple through addition of diethyl ether to the reaction mixture and centrifugations. Full characterization of the nano-Pd(0)/DPPPEG200 was performed by XRD spectra, UV-Vis spectra, and also by TEM image. This nano-complex was used as an efficient catalyst for copper-free Sonogashira and homocoupling reactions of aryl halides. The sonogashira reaction of aryl halides was conducted at 80 °C in PEG. However, the homocoupling reaction was performed at 100 °C for aryl iodides and activated aryl bromides and at 130 °C for deactivated aryl bromides and aryl chlorides in PEG. The catalyst was recovered and recycled for four consecutive runs.
- Iranpoor, Nasser,Firouzabadi, Habib,Riazi, Asma
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p. 155 - 165
(2015/07/20)
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- The fight against the influenza A virus H1N1: Synthesis, molecular modeling, and biological evaluation of benzofurazan derivatives as viral RNA polymerase inhibitors
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The influenza RNA polymerase complex, which consists of the three subunits PA, PB1, and PB2, is a promising target for the development of new antiviral drugs. A large library of benzofurazan compounds was synthesized and assayed against influenza virus A/WSN/33 (H1N1). Most of the new derivatives were found to act by inhibiting the viral RNA polymerase complex through disruption of the complex formed between subunits PA and PB1. Docking studies were also performed to elucidate the binding mode of benzofurazans within the PB1 binding site in PA and to identify amino acids involved in their mechanism of action. The predicted binding pose is fully consistent with the biological data and lays the foundation for the rational development of more effective PA-PB1 inhibitors. In the fight against influenza virus A/WSN/33 (H1N1), the PA-PB1 protein-protein interaction is emerging as a new drug target. To identify small molecules able to inhibit the viral RNA polymerase complex, the benzofurazan scaffold was explored by synthesizing a large library of derivatives. Some compounds showed high anti-H1N1 activity and emerged as effective inhibitors of the PA-PB1 interaction, with IC50 values in the micromolar range. Copyright
- Pagano, Mafalda,Castagnolo, Daniele,Bernardini, Martina,Fallacara, Anna Lucia,Laurenzana, Ilaria,Deodato, Davide,Kessler, Ulrich,Pilger, Beatrice,Stergiou, Lilli,Strunze, Stephan,Tintori, Cristina,Botta, Maurizio
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p. 129 - 150
(2014/01/17)
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- Palladium supported on zinc oxide nanoparticles: Synthesis, characterization, and application as heterogeneous catalyst for Mizoroki-Heck and Sonogashira reactions under ligand-free and air atmosphere conditions
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In this paper, a novel Palladium (Pd) supported on ZnO nanoparticles was readily synthesized and characterized by using X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and BET specific surface area measurement. The total amount of palladium particles on ZnO was determined by induced coupled plasma (ICP) analysis and atomic absorption spectroscopy (AAS) which is 9.8 wt%. Percentage of accessible Pd as active catalyst is also estimated to 2.72% based on the thermogravimetric (TG) analysis. Nano Pd/ZnO was found as a new, novel, and excellent heterogeneous catalyst for ligand-free C-C bond formation through the Mizoroki-Heck and Sonogashira reactions under air atmosphere without the use of any Ar or N2 flow. The catalyst can be recovered and recycled several times without marked loss of activity.
- Hosseini-Sarvari, Mona,Razmi, Zahra,Doroodmand, Mohammad Mehdi
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p. 477 - 486
(2014/03/21)
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- Cross-coupling reactions catalyzed by an N-heterocyclic carbene-Pd(ii) complex under aerobic and CuI-free conditions
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A Pd-complex, (Cat. 3), has been successfully employed as a highly efficient and recyclable catalyst for the Sonogashira and Heck reactions of aryl bromides with various terminal acetylenes and olefins. The catalytic reactions proceed with excellent yields with a low catalyst loading (1.0 mol%) under aerobic and CuI-free conditions. A plausible mechanism has also been proposed for the reaction. the Partner Organisations 2014.
- Lu, Hongfei,Wang, Lin,Yang, Feifei,Wu, Runze,Shen, Wei
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p. 30447 - 30452
(2014/08/05)
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- Phenoxide-mediated Sonogashira coupling of trimethylsilylalkynes and aryliodides: Practical synthesis of phenolic-hydroxy-substituted diarylethynes and 1,4-diarylbutadiynes
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We successfully synthesized phenolic-hydroxy-substituted diarylethynes and 1,4-diarylbutadiynes from trimethylsilylalkynes and aryliodides via silyl-group-migration-induced deprotection of alkynes and the usual Sonogashira coupling. The phenol moiety, which works as a desilylating agent, can be attached to any position in the coupling partner. This improvement for Sonogashira coupling would be highly effective, especially when the coupling partner has a phenol moiety. Additionally, the stability of the migrated silyl moiety on the ethynylation of 2-iodophenol is discussed.
- Shigeta, Masayuki,Watanabe, Junji,Konishi, Gen-Ichi
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supporting information
p. 1761 - 1764
(2013/04/10)
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- Regioselectivity of Larock heteroannulation: A contribution from electronic properties of diarylacetylenes
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A series of 2,3-diarylindoles were synthesized from 2-iodoaniline and unsymmetrical diarylacetylenes using the Larock heteroannulation. Diarylacetylenes bearing electron-withdrawing substituents lead to 2,3-diarylindoles with substituted phenyl moieties at the 2-position as major products, while those with electron-donating groups preferably yield indole products with substituted phenyl moieties at the 3-position. The regioisomeric product ratios exhibit a clear correlation with Hammett σp values. DFT calculations reveal the origin of this effect, displaying smaller activation energy barriers for those pathways leading to the major regioisomer.
- Phetrak, Nared,Rukkijakan, Thanya,Sirijaraensre, Jakkapan,Prabpai, Samran,Kongsaeree, Palangpon,Klinchan, Chayada,Chuawong, Pitak
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p. 12703 - 12709
(2014/01/17)
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- Systematic investigation of silver-carbon bonding in coordination frameworks with aryl ligands that contain ethynyl and ethenyl substituents
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Single-crystal X-ray diffraction of a series of ten crystalline silver(I)-trifluoroacetate complexes that contained designed ligands, each of which was composed of an aromatic system that was functionalized with terminal and internal ethynyl groups and a
- Hau, Sam C. K.,Mak, Thomas C. W.
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supporting information
p. 5387 - 5400
(2013/05/23)
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- Chelidamic acid functionalized stimuli-responsive hydrogel supported-palladium catalyst for copper-free Sonogashira reaction in aqueous media
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A thermo and pH-responsive hydrogel (PNIPAM-co-PPAP) was synthesized via free radical polymerization of N-isopropylacrylamide (NIPAM) and potassium 4-(acryloyloxy) pyridine-2, 6-dicarboxylate (PAP) in mixed solvents of water and tetrahydrofuran. SEM micro
- Yang, Jianhua,Zhang, Xi,Yu, Wei,Liu, Weijie,Bian, Fengling
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p. 710 - 718
(2013/06/26)
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- Palladium-poly(3-aminoquinoline) hollow-sphere composite: Application in sonogashira coupling reactions
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We report on the use of palladium acetate for the synthesis of a palladium-based polymer composite material as a catalyst for Sonogashira cross-coupling reactions for aryl and heteroaryl of iodides and bromides.
- UlIslam, Rafique,Mahato, Sanjit K.,Shukla, Sudheesh K.,Witcomb, Michael J.,Mallick, Kaushik
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p. 2453 - 2461
(2013/08/23)
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- Practical synthesis of unsymmetrical diarylacetylenes from propiolic acid and two different aryl bromides
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A palladium catalyst that mediates the one-pot sequential Sonogashira and decarboxylative coupling of propiolic acid with two different aryl bromides has been developed. Selective coupling of the first aryl bromide was achieved in the presence of a copper-free, monometallic catalyst generated in situ from allylpalladium chloride dimer and SPhos with tetra-n-butylammonium fluoride as the base in an N-methyl-2-pyrrolidone/water solvent mixture. Upon addition of another aryl bromide and raising the temperature from 50 to 80°C, the intermediate arylpropiolic acid underwent decarboxylative coupling to give the corresponding diarylacetylene. Thus, the new system permits a one-pot three-component synthesis of unsymmetrical diarylacetylenes from widely available aryl bromides, rather than expensive aryl iodides, and propiolic acid, rather than (trimethylsilyl)acetylene, as an inexpensive and easy-to-handle acetylene synthon. The process is highly selective, modular, and gives access to a wide range of unsymmetrical diarylacetylenes in good yields. A palladium-catalyzed three component synthesis of diaryl acetylenes has been optimized. Several disubstituted alkynes have been prepared from two different arylbromides and propiolic acid in good yields. Copyright
- Tartaggia, Stefano,De Lucchi, Ottorino,Goossen, Lukas J.
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supporting information; experimental part
p. 1431 - 1438
(2012/04/04)
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- Photo-induced sonogashira C-C coupling reaction catalyzed by simple copper(I) chloride salt at room temperature
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The conventional thermal Sonogashira C-C coupling reaction requires the use of a palladium catalyst and a large amount of ligands. Although there were a few reports describing the use of inexpensive metal catalysts, such as, copper (Cu), iron (Fe), and nickel (Ni), for replacement of palladium (Pd) in the Sonogashira reactions, it was later questioned that the observed effects were due to ppb levels contamination of Pd present in the reagents used in the reactions. Herein, we report that simple copper(I) chloride (CuCl) salt, in the absence of Pd and ligands, can catalyze the Sonogashira reaction with high yields (80-99%) under blue LED light irradiation at room temperature. Control experiments show that no cross-coupling product was formed, when palladium(II) chloride (PdCl2) was used to replace CuCl as a catalyst. A series of electron-rich and electron-poor substituted aryl halides (bromides and iodides) as well as aryl- and alkylacetylenes are examined and the reaction mechanism is discussed.
- Sagadevan, Arunachalam,Hwang, Kuo Chu
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supporting information
p. 3421 - 3427
(2013/02/22)
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- Lyotropic chiral nematic liquid crystalline aliphatic conjugated polymers based on disubstituted polyacetylene derivatives that exhibit high dissymmetry factors in circularly polarized luminescence
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We synthesized disubstituted liquid crystalline polyacetylene (diLCPA) derivatives bearing 4-nonyloxy phenyl groups with lyotropic and thermotropic LC behavior. The poly(diphenylacetylene) main chain structure of the diLCPAs and the chirality induced with either chiral moieties or chiral dopants allow the formation of a highly ordered lyotropic N*-LC phase. Circular dichroism (CD) spectra of the diLCPAs imply that one-handed intrachain helical structures are formed in solution, while interchain helical π-stacking between the polymer main chains are formed in cast film and in the N*-LC state. Absorption dissymmetry factors (gabs) in the N*-LC state show values on the order of 10-1. The N*-LC state facilitates the formation of helically π-stacked structures with a high degree of helical ordering of the diLCPA and is indispensable for the generation of circularly polarized luminescence (CPL) with high emission dissymmetry factors (g em) on the order of 10-1. To the best of our knowledge, this is the highest reported value of CPL achieved for aliphatic, conjugated polymers. As an alternative to the thermotropic N*-LC phase, we have found that the lyotropic N*-LC phase of diLCPA could be promising materials possessing CPL functionality for use in next-generation π-conjugated organic optoelectronic devices, displays, and sensors.
- San Jose, Benedict A.,Matsushita, Satoshi,Akagi, Kazuo
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supporting information
p. 19795 - 19807
(2013/02/22)
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- Dimeric ortho-palladated homoveratrylamine as an efficient homogeneous catalyst for copper-free Sonogashira cross-coupling reaction
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The catalytic activity of ortho-palladated [Pd{C6H2(CH2CH2NH2)-(OMe)2,3,4} (m-Br)]2, a complex of homoveratrylamine in the copper-free Sonogashira coupling reaction has been investigated. This complex is a catalyst that is efficient, stable and non-sensitive to air and moisture in the Sonogashira reaction. In this homogeneous catalytic system, various aryl halides were efficiently coupled with phenylacetylene in mostly moderate to good yields in N-methylpyrrolidone at 100 °C under copper-free conditions. Copyright
- Hajipour, Abdol R.,Rahimi, Hannaneh,Rafiee, Fatemeh
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p. 727 - 730
(2013/02/22)
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- Helical and luminescent disubstituted polyacetylenes: Synthesis, helicity, and light emission of poly(diphenylacetylene)s bearing chiral menthyl pendant groups
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Diphenylacetylenes containing chiral menthyl groups [C6H 5C=C-C6H4OCOCH2OR* and C 6H5C=C-C6H4CO2R*, R* = (1R,2S,5R)-(-)-menthyl] are synthesized
- Jim, Cathy K. W.,Lam, Jacky W. Y.,Leung, Chris W. T.,Qin, Anjun,Mahtab, Faisal,Tang, Ben Zhong
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experimental part
p. 2427 - 2437
(2012/03/26)
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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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