- Palladium-catalyzed cross-coupling reactions of triarylbismuthanes with terminal alkynes under aerobic conditions
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Abstract A simple Pd-catalyzed Sonogashira-type cross-coupling reaction using of triarylbismuthanes is described. The reaction of triarylbismuthanes with terminal alkynes in the presence of 5 mol% of Pd(OAc)2, 6 equiv. AgF and 6 equiv. K3PO4 at room temperature afforded the coupling products in good to excellent yield. The reaction proceeded effectively under aerobic conditions, and all three aryl groups on bismuth could be transferred to the coupling products. The reaction was sensitive to the electronic nature of the triarylbismuthanes: substrates bearing an electron-withdrawing group on the aromatic ring showed higher reactivity than those having an electron-donating group.
- Matsumura, Mio,Yamada, Mizuki,Tsuji, Toshiyuki,Murata, Yuki,Kakusawa, Naoki,Yasuike, Shuji
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- Oxine based unsymmetrical (O?, N, S/Se) pincer ligands and their palladium(ii) complexes: synthesis, structural aspects and applications as a catalyst in amine and copper-free Sonogashira coupling
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Unsymmetrical pincer ligands having an 8-hydroxyquinoline (oxine) core viz. 2-(phenylthio/selenomethyl) quinolin-8-ol (L1/L2), 2-(N,N-dimethylthiocarbamoyl) quinolin-8-ol (L3) and 2-(pyrrolidin-1-ylthiocarbamoyl) quinolin-8-ol (L4) were synthesized. 2-Met
- Kumar, Satyendra,Saleem, Fariha,Mishra, Manish Kumar,Singh, Ajai K.
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- Carboxylate-based, room-temperature ionic liquids as efficient media for palladium-catalyzed homocoupling and sonogashira-hagihara reactions of aryl halides
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Carboxylate-based salts are introduced as easily prepared, cheap and stable ionic liquids (ILs) that act as the base, ligand, reducing agent and media for the efficient phosphane-free, palladium-catalyzed homocoupling reaction of aryl iodides and bromides. The efficient copper and phosphane-free Sonagashira coupling reaction of aryl iodides and bromides is also demonstrated in these ILs. One of the ILs was also phosphorylated and showed high efficiency and recyclability as a medium, and was also used as a ligand for palladium-catalyzed homocoupling and copper-free Sonogashira reactions of aryl iodides and bromides. Copyright
- Iranpoor, Nasser,Firouzabadi, Habib,Ahmadi, Yasaman
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- Gelatin as a bioorganic reductant, ligand and support for palladium nanoparticles. Application as a catalyst for ligand- and amine-free Sonogashira-Hagihara reaction
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Palladium nanoparticles were deposited and reduced by gelatin as a safe edible, naturally occurring and cheap support. No extra reducing agents were used for the generation of Pd(0) nanoparticles from the Pd(ii) salt. The nanoparticles of Pd supported on
- Firouzabadi, Habib,Iranpoor, Nasser,Ghaderi, Arash
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- Transition-Metal-Free Sonogashira-Type Coupling Reactions in Water
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Microwave-assisted transition-metal-free Sonogashira-type coupling reactions are described. The reactions are run in water as the sole solvent, without the need for copper(I) or any transition-metal-phosphane complex. The scope of the methodology was tested by reaction of a wide variety of aryl halides and heteroaryl halides. The reaction was also investigated under conventional heating conditions. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
- Appukkuttan, Prasad,Dehaen, Wim,Van Der Eycken, Erik
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- Facile synthesis of acetylene-substituted terthiophenes
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A modified Horner-Emmons condensation reaction has been employed for the synthesis of acetylene-substituted terthiophenes in excellent yields. Conjugating 3′-aryl substituents to terthiophene using an ethyne rather than an ethene linker results in enhance
- Wagner, Pawel,Partridge, Ashton C.,Jolley, Kenneth W.,Officer, David L.
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- An efficient ligand- and copper-free Sonogashira reaction catalyzed by palladium nanoparticles supported on pectin
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A novel and green procedure for synthesis of Palladium nanoparticles (2-6 nm) supported on pectin, as a reductant and ligand is described. The synthesized catalyst was further successfully explored in copper, ligand-and amine-free Sonogashira-Hagihara cou
- Khazaei, Ardeshir,Rahmati, Sadegh,Saednia, Shahnaz
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- Recyclable palladium-catalyzed Sonogashira-Hagihara coupling of aryl halides using 2-aminophenyl diphenylphosphinite ligand in neat water under copper-free condition
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An efficient heterogeneous copper-free Sonogashira-Hagihara coupling reaction was performed in the presence of 2-aminophenyl diphenylphosphinite (L) as a ligand, Pd(OAc)2 and a base in neat water at 25-95 °C. By this protocol, different aryl ha
- Firouzabadi, Habib,Iranpoor, Nasser,Gholinejad, Mohammad
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- Efficient and General Protocol for the Copper-Free Sonogashira Coupling of Aryl Bromides at Room Temperature
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(Equation presented) A mild and general protocol for the copper-free Sonogashira coupling of aryl bromides with acetylenes has been developed. The use of (AllylPdCl)2 and P(t-Bu)3 provides the active Pd(0) catalyst that allows subseq
- Soheili, Arash,Albaneze-Walker, Jennifer,Murry, Jerry A.,Dormer, Peter G.,Hughes, David L.
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- The first regioselective hydroformylation of acetylenic thiophenes catalyzed by a zwitterionic rhodium complex and triphenyl phosphite
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The hydroformylation of acetylenic thiophenes is readily accomplished by using the zwitterionic rhodium catalyst (η6-C6H5BPh3)-Rh+(1,5-COD) and triphenyl phosphite in the presence of CO and H2. This catalytic system affords, as the major product, the *β-unsaturated aldehyde with the aldehyde and thiophene attached to the same olefin carbon atom. Assistance of sulfur from the heterocycle provides excellent regioselectivity and yields when the acetylenic unit is a propargyl ether or ester, phenylacetylene, or an enyne.
- Van Den Hoven, Bernard G.,Alper, Howard
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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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- A facile protocol for copper-free palladium-catalyzed Sonogashira coupling in aqueous media
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The combination of a readily available palladium catalyst and an eco-friendly basic aqueous solution of room-temperature ionic liquid, choline hydroxide (ChOH), was used in a facile protocol alternative to the Sonogashira coupling reaction, alkynylation of aryl halides in the absence of a copper cocatalyst and an external base. The dual nature of ChOH to act as a base and a green solvent played a crucial role in the catalytic cycle. The coupling reaction progressed efficiently to form a Csp-Csp2 bond under the identified conditions although the reaction outcome depended significantly on the substrates.
- Jung, Da-Young,Park, Soo Youl,Kim, Seung-Hoi
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supporting information
p. 110 - 116
(2021/11/09)
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- Decarbonylative Sonogashira Cross-Coupling of Carboxylic Acids
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Decarbonylative Sonogashira cross-coupling of carboxylic acids by palladium catalysis is presented. The carboxylic acid is activated in situ by the formation of a mixed anhydride and further decarbonylates using the Pd(OAc)2/Xantphos system to provide an aryl-Pd intermediate, which is intercepted by alkynes to access the traditional Pd(0)/(II) cycle using carboxylic acids as ubiquitous and orthogonal electrophilic cross-coupling partners. The methodology efficiently constructs new C(sp2)-C(sp) bonds and can be applied to the derivatization of pharmaceuticals. Mechanistic studies give support to decarbonylation preceding transmetalation in this process.
- Liu, Chengwei,Szostak, Michal
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supporting information
p. 4726 - 4730
(2021/06/28)
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- Glycosyl Triazole Ligand for Temperature-Dependent Competitive Reactions of Cu-Catalyzed Sonogashira Coupling and Glaser Coupling
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Glycosyl triazoles have been introduced as efficient ligands for the Cu-catalyzed Sonogashira reaction to overcome the challenges of sideways homocoupling reactions in Cu catalysis in this reaction. The atmospheric oxygen in a sealed tube did not affect t
- Mishra, Nidhi,Singh, Sumit K.,Singh, Anoop S.,Agrahari, Anand K.,Tiwari, Vinod K.
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p. 17884 - 17895
(2021/12/17)
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- Shuttling Catalyst: Facilitating C?C Bond Formation via Cross-Couplings with a Thermoresponsive Polymeric Ligand
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A poly(ethylene glycol) (PEG) linked ortho-MeO-phenyldicyclohexylphosphine (MeO-WePhos) ligand has been synthesized to promote Pd-catalyzed carbon-carbon bond formation by cross-couplings including Sonogashira, Heck, Hiyama and Stille reactions, providing corresponding (hetero)aryl substituted alkynes, alkenes and bi(hetero)aryls in good to excellent isolated yields with low Pd loadings. Facilitated by the lower critical solution temperature behaviour of the polymeric monophosphine ligand, the metal-complex could rapidly shuttle between organic and water phases as regulated by temperature, enabling highly efficient catalyst recycling via a simple phase separation. The chemical structure of ligand was determined by matrix-assisted laser desorption/ionization-time of flight mass spectrometry, nuclear magnetic resonance spectrometry and size-exclusion chromatography measurements. Notably, as demonstrated by the inductively coupled plasma-atomic emission spectrometry measurement, 98% Pd was kept in the water phase after 6 cycles of catalyst recycling experiments. Given the profound impact of transition-metal-catalyzed covalent bond formation and the increasing demand of sustainable chemistry, this work provides an alternative method to conduct cross-couplings with a polymeric shuttling catalyst.
- Wang, Erfei,Zhang, Jiawei,Zhong, Zhuoran,Chen, Kaixuan,Chen, Mao
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p. 419 - 423
(2020/01/08)
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- A new approach to large scale production of dimethyl sulfone: A promising and strong recyclable solvent for ligand-free Cu-catalyzed C-C cross-coupling reactions
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Dimethyl sulfone (DMSN) was easily prepared through efficient oxidation of dimethyl sulfoxide (DMSO) and used as a strong and green solvent for organic reactions. A mixture of HNO3/NaOCl was used as an oxidizing agent for efficient oxidation of DMSO to DMSN. The effect of DMSN was evaluated for copper-catalyzed coupling reactions. It is worth noting that DMSN could play the role of a ligand for copper ions. A general survey was accomplished for various types of C-C cross-coupling reactions catalyzed by CuI in DMSN in the absence of any ligand. Moderate to good yields were achieved for Sonogashira, Heck, and Suzuki cross-coupling reactions. Finally, DMSN was recovered and reused for several consecutive runs without any loss of its activity.
- Cheng, Shen,Wei, Wei,Zhang, Xingyu,Yu, Hewei,Huang, Mingming,Kazemnejadi, Milad
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p. 2069 - 2076
(2020/04/07)
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- Ruthenium-Catalyzed E-Selective Alkyne Semihydrogenation with Alcohols as Hydrogen Donors
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Selective direct ruthenium-catalyzed semihydrogenation of diaryl alkynes to the corresponding E-alkenes has been achieved using alcohols as the hydrogen source. The method employs a simple ruthenium catalyst, does not require external ligands, and affords the desired products in > 99% NMR yield in most cases (up to 93% isolated yield). Best results were obtained using benzyl alcohol as the hydrogen donor, although biorenewable alcohols such as furfuryl alcohol could also be applied. In addition, tandem semihydrogenation-alkylation reactions were demonstrated, with potential applications in the synthesis of resveratrol derivatives.
- Ekebergh, Andreas,Begon, Romain,Kann, Nina
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p. 2966 - 2975
(2020/03/04)
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- One-Pot Conversion of Aldehydes and Aryl Halides to Disubstituted Alkynes via Tandem Seyferth-Gilbert Homologation/Copper-Free Sonogashira Coupling
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A practically convenient protocol has been developed to convert a mixture of an aldehyde, aryl halide, and the Bestmann-Ohira reagent into disubstituted acetylene via a successive addition of base (Cs2CO3) and a Pd(II) catalyst, allowing sufficient time after addition of each of these reagents for the tandem processes (Seyferth-Gilbert homologation and Sonogashira coupling) to occur. Notably, for the latter reaction, no copper catalyst was required.
- Sapegin, Alexander,Krasavin, Mikhail
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p. 8788 - 8795
(2019/07/03)
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- Sonogashira Cross-Coupling of Aryltrimethylammonium Salts
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A protocol for C(sp)-C(sp2) bond formation via the Sonogashira coupling reaction involving C-N bond cleavage with aryltrimethylammonium triflate as an electrophilic coupling partner is described in this work. The reactions proceeded well under mild conditions with a stoichiometric ratio of alkyl, aryl, or heteroaryl acetylenes and provided yields of up to 93%. Numerous useful functional groups were tolerated under the reaction conditions. Direct amine alkynylation can be achieved through a one-pot process without the isolation of ammonium salt. The protocol can be performed on a gram scale. Density functional theory calculations were performed to investigate the reaction mechanism that involved oxidative addition, alkyne coordination, deprotonation, and reductive elimination, which yielded the cross-coupling product.
- Chen, Qianwei,Gao, Fengchen,Tang, Huiling,Yao, Miao,Zhao, Qian,Shi, Yanhui,Dang, Yanfeng,Cao, Changsheng
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p. 3730 - 3736
(2019/04/13)
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- Green, cost-effective and efficient procedure for Heck and Sonogashira coupling reactions using palladium nanoparticles supported on functionalized Fe3O4@SiO2 by polyvinyl alcohol as a highly active, durable and reusable catalyst
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A novel heterogenized organometallic catalyst was synthesized by coordinating palladium with polyvinyl alcohol-functionalized Fe3O4@SiO2 nanospheres. This novel catalyst was characterized using Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscope, field emission scanning electron microscope, dynamic light scattering, UV–vis spectroscopy, X-ray photoelectron spectroscopy, energy dispersive X-ray analysis, thermogravimetric analysis and inductively coupled plasma analysis. The prepared palladium nanoparticles supported on polyvinyl alcohol functionalized Fe3O4@SiO2 nanoparticles were successfully applied as a magnetically recyclable catalyst in Heck and Sonogashira coupling reactions in water. They showed remarkable activity toward aryl halides (I, Br, Cl) using very low palladium loading in excellent yields and demonstrated high TONs (mmol of product per mmol of catalyst). Also, the catalyst could be magnetically separated and reused seven times without any appreciable loss of catalytic activity.
- Sardarian, Ali Reza,Eslahi, Hassan,Esmaeilpour, Mohsen
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- Bis-salophen palladium complex immobilized on Fe3O4@SiO2 nanoparticles as a highly active and durable phosphine-free catalyst for Heck and copper-free Sonogashira coupling reactions
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New Fe3O4@SiO2 core-shell superparamagnetic nanoparticles functionalized by a bis-salophen Schiff base Pd complex were synthesized and employed as an efficient magnetic nanocatalyst in the Heck and Sonogashira cross coupling reactions. The synthesized nanostructures were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), dynamic light scattering (DLS), energy dispersive X-ray analysis (EDX), X-ray photoelectron spectroscopy (XPS), elemental analysis (CHN), cyclic voltammetry (CV), Brunauer-Emmett-Teller analysis (BET), and UV-vis spectroscopy. The morphology and size of the nanoparticles were investigated by FE-SEM and TEM analyses. Furthermore, the magnetic properties of the catalyst were investigated by VSM analysis. The loading content and leaching amounts of palladium on the catalyst were measured by inductively coupled plasma (ICP) analysis. Also, the thermal behavior of this magnetic heterogeneous catalyst was studied using a TGA instrument. This heterogeneous catalytic system showed a good performance in the coupling of aryl halides with alkynes (Sonogashira reaction) as well as aryl halides with alkene derivatives (Heck reaction). High to excellent yields were achieved for these C-C coupling reactions. The catalyst can be simply separated from the reaction media by an external magnet and reused for eight consecutive runs without any significant loss of activity. Finally, the kinetics of the reactions were studied in this work.
- Sardarian, Ali Reza,Kazemnejadi, Milad,Esmaeilpour, Mohsen
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p. 3132 - 3145
(2019/03/06)
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- Highly efficient synthesis of 1,2-disubstituted acetylenes derivatives from the cross-coupling reactions of 1-bromoalkynes with organoalane reagents
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A Highly efficient route for the synthesis of 1,2-disubstituted acetylene derivatives has been developed by palladium catalyzed cross-couplings of alkynyl halides with (hetero)aryl aluminium reagents under mild conditions. This has given corresponding cross-coupling products good to excellent isolated yields of up to 99%. The aryls bearing electron-donating or electron-withdrawing groups in either alkynylhalides or arylaluminum substrates gave cross-coupling products good yields. This process was simple and easily performed, which provides an efficient method for the synthesis of 1,2-disubstituted acetylenes derivatives. On the basis of the experimental results, a possible catalytic cycle has been proposed.
- Shao, Xue-Bei,Jiang, Xin,Li, Qing-Han,Zhao, Zhi-Gang
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p. 6063 - 6070
(2018/09/12)
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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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- 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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- C-S Bond Alkynylation of Diaryl Sulfoxides with Terminal Alkynes by Means of a Palladium-NHC Catalyst
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Sonogashira-Hagihara-type alkynylation of diaryl sulfoxides with unactivated terminal alkynes has been developed. With a combination of a palladium-NHC catalyst and LiO t Bu as a base, a series of diaryl sulfoxides were converted into the alkynylated products via C-S bond cleavage.
- Yoshida, Yuto,Nogi, Keisuke,Yorimitsu, Hideki
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supporting information
p. 2561 - 2564
(2017/11/16)
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- Sonogashira reaction using arylsulfonium salts as cross-coupling partners
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Triarylsulfonium, alkyl- and fluoroalkyl(diaryl)-sulfonium, and aryl(dialkyl)sulfonium triflates are successfully used as a new family of cross-coupling participants in the Sonogashira reaction as aryldiazonium, diaryliodonium, and tetraphenylphosphonium salts. It was found that terminal alkynes reacted mildly with triarylsulfonium or (2,2,2-trifluoroethyl)diphenylsulfonium triflate at room temperature under Pdand Cu-cocatalysis to give the corresponding arylalkynes in up to >99% yield. This protocol represents the first use of arylsulfonium salts as cross-coupling partners in the Pd/Cu-catalyzed Sonogashira reaction.
- Tian, Ze-Yu,Wang, Shi-Meng,Jia, Su-Jiao,Song, Hai-Xia,Zhang, Cheng-Pan
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p. 5454 - 5457
(2017/11/06)
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- Ligand- and copper-free Sonogashira and Heck couplings of (Het)aryl chlorides and bromides catalyzed by palladium nanoparticles supported on in situ generated Al(OH)3
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The ligand- and copper-free Sonogashira reaction of (Het)aryl halides (Br and Cl) with various terminal alkynes and the Heck coupling of (Het)aryl halides (Br and Cl) with a series of olefins, catalyzed by palladium nanoparticles supported on newly generated Al(OH)3, were developed. The catalyst can be readily recovered and reused 6 times without significant loss of activity and palladium leaching.
- Li, Xing,Gong, Xiaolei,Li, Zhipeng,Chang, Honghong,Gao, Wenchao,Wei, Wenlong
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p. 2475 - 2479
(2017/02/05)
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- Direct preparation of arylethynylzinc bromides and their application to cross-coupling reactions
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A novel synthetic protocol for the preparation of arylethynylzinc bromides has been developed. Thus-obtained organozinc reagents were successfully employed in the subsequent cross-coupling reactions with a broad range of aryl halides providing the corresponding alkynylated compounds in good to excellent yields.
- Joo, Seong-Ryu,Kim, Jong-Sung,Kim, Seung-Hoi
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p. 3267 - 3270
(2017/07/27)
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- A straightforward alkynylation of Li and Mg metalated heterocycles with sulfonylacetylenes
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Coupling of alkynyl moieties to heterocyclic rings, without using transition metals, can be easily performed by the reaction of aryl or heteroaryl sulfonylacetylenes with heteroaryl-Li compounds or their corresponding less reactive magnesium derivatives.
- Marzo, Leyre,Prez, Ignacio,Yuste, Francisco,Alemn, Jos,Garca Ruano, Jos Luis
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supporting information
p. 346 - 349
(2015/02/05)
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- Palladium catalyst supported on PEGylated imidazolium based phosphinite ionic liquid-modified magnetic silica core-shell nanoparticles: A worthy and highly water-dispersible catalyst for organic reactions in water
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A highly water-dispersible palladium nanocatalyst was fabricated by the immobilization of Pd onto the surface of PEGylated imidazolium based phosphinite ionic liquid functionalized γ-Fe2O3@SiO2 core-shell nanoparticles. This nanocatalyst (denoted as [Pd@PEGylated ImIL-OPPh2-γ-Fe2O3@SiO2]) was assessed as a promising Pd catalyst in different organic reactions including Mizoroki-Heck and Sonogashira coupling reactions of aryl halides and the reduction reaction of 4-nitrophenol (4NP) to 4-aminophenol (4AP). From the application point of view, this nanocatalyst showed high thermal versatility, stability, recoverability, and compatibility in aqueous media. The catalyst recovery test revealed that its performance and catalytic activity stayed indefectible during several sequential runs. The loading level of Pd in the [Pd@PEGylated ImIL-OPPh2-γ-Fe2O3@SiO2] catalyst was 0.087 mmol g-1. Pivotal properties including high robustness, efficiency and turnover frequency (TOF), mild reaction conditions, utilization of water as a green solvent, simple product work-up, and facile catalyst recovery make this catalyst favourable from the environmental and economic points of view.
- Bahadorikhalili, Saeed,Ma'mani, Leila,Mahdavi, Hossein,Shafiee, Abbas
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p. 71297 - 71305
(2015/09/08)
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- Nano palladium supported on high-surface-area metal-organic framework MIL-101: An efficient catalyst for Sonogashira coupling of aryl and heteroaryl bromides with alkynes
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Palladium nanoparticle-incorporated metal-organic framework MIL-101 (Pd/MIL-101) was successfully synthesized and characterized using X-ray diffraction, nitrogen physisorption, X-ray photoelectron, UV-visible and infrared spectroscopies, and transmission electron microscopy. The characterization techniques confirmed high porosity and high surface area of MIL-101 and high stability of nano-size palladium particles. Pd/MIL-101 nanocomposite was investigated for the Sonogashira cross-coupling reaction of aryl and heteroaryl bromides with various alkynes under copper-free conditions. The reusability of the catalyst was tested for up to four cycles without any significant loss in catalytic activity.
- Annapurna, Manne,Parsharamulu,Vishnuvardhan Reddy,Suresh,Likhar, Pravin R.,Lakshmi Kantam, Mannepalli
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p. 234 - 239
(2015/03/30)
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- Synthesis of 4-sulfonatobenzylphosphines and their application in aqueous-phase palladium-catalyzed cross-coupling
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Aqueous-biphasic catalysis offers the potential for safer and more environmentally sustainable synthetic processes. In addition, hydrophilic supporting ligands allow homogeneous catalysts to be readily separated from organic products and potentially reused. The synthesis of two new water-soluble ligand precursors, di-tert-butyl(4-sulfonatobenzyl)phosphonium and di-1-adamantyl(4-sulfonatobenzyl)phosphonium, are reported. The air-stable, zwitterionic phosphonium salts were prepared by the reaction of dialkylphosphines with ethyl 4-bromomethylbenzenesulfonate, which results in a one-pot alkylation followed by deprotection of the ethyl sulfonate. This methodology provides an operationally simpler route to sulfonated benzylphosphines than electrophilic sulfonation. The new phosphine ligands were applied to aqueous-phase Suzuki and Sonogashira couplings of aryl bromides.
- Moore, Jane N.,Laskay, Nicholas M.,Duque, Kevin S.,Kelley, Steven P.,Rogers, Robin D.,Shaughnessy, Kevin H.
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supporting information
p. 16 - 24
(2015/02/05)
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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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- Ligand-Assisted Gold-Catalyzed Cross-Coupling with Aryldiazonium Salts: Redox Gold Catalysis without an External Oxidant
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Gold-catalyzed C(sp)-C(sp2) and C(sp2)-C(sp2) cross-coupling reactions are accomplished with aryldiazonium salts as the coupling partner. With the assistance of bpy ligand, gold(I) species were oxidized to gold(III) by diazonium without any external oxidants. Monitoring the reaction with NMR and ESI-MS provided strong evidence for the nitrogen extrusion followed by AuIII reductive elimination as the key step.
- Cai, Rong,Lu, Mei,Aguilera, Ellen Y.,Xi, Yumeng,Akhmedov, Novruz G.,Petersen, Jeffrey L.,Chen, Hao,Shi, Xiaodong
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p. 8772 - 8776
(2015/11/27)
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- Synthesis of 4-sulfonatobenzylphosphines and their application in aqueous-phase palladium-catalyzed cross-coupling
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Aqueous-biphasic catalysis offers the potential for safer and more environmentally sustainable synthetic processes. In addition, hydrophilic supporting ligands allow homogeneous catalysts to be readily separated from organic products and potentially reused. The synthesis of two new water-soluble ligand precursors, di-tert-butyl(4-sulfonatobenzyl)phosphonium and di-1-adamantyl(4-sulfonatobenzyl)phosphonium, are reported. The air-stable, zwitterionic phosphonium salts were prepared by the reaction of dialkylphosphines with ethyl 4-bromomethylbenzenesulfonate, which results in a one-pot alkylation followed by deprotection of the ethyl sulfonate. This methodology provides an operationally simpler route to sulfonated benzylphosphines than electrophilic sulfonation. The new phosphine ligands were applied to aqueous-phase Suzuki and Sonogashira couplings of aryl bromides.
- Moore, Jane N.,Laskay, Nicholas M.,Duque, Kevin S.,Kelley, Steven P.,Rogers, Robin D.,Shaughnessy, Kevin H.
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supporting information
p. 16 - 24
(2015/01/09)
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- Ligand-free copper-catalyzed cross-coupling reaction of alkynes with aryl iodides and vinyl halides
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A copper-catalyzed cross-coupling reaction of alkynes with aryl iodides is described. The system tolerates a broad range of functional groups and enables the sterically demanding substrates presented during the catalysis with only 5-10 mol% of Cu2O as the catalyst. Georg Thieme Verlag Stuttgart. New York.
- Tsai, Wan-Ting,Lin, Yun-Yung,Chen, Yi-An,Lee, Chin-Fa
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supporting information
p. 443 - 447
(2014/03/21)
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- Synthesis and characterization of Fe3O4@SiO 2-polymer-imid-Pd magnetic porous nanospheres and their application as a novel recyclable catalyst for Sonogashira-Hagihara coupling reactions
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We demonstrate herein the modification of magnetic nanoparticles and their use as a magnetic nanocatalyst in direct coupling reactions of aryl halides with terminal alkynes. Magnetite particles were prepared by simple co-precipitation method in aqueous me
- Mohsen, Esmaeilpour,Jaber, Javidi,Mehdi, Mokhtari Abarghoui,Fatemeh, Nowroozi Dodeji
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p. 499 - 510
(2014/04/03)
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- Design and synthesis of a new phosphinite-functionalized clay composite for the stabilization of palladium nanoparticles. Application as a recoverable catalyst for C-C bond formation reactions
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A new clay composite carrying phosphinite-functionalized ionic liquid moieties (CCPIL) has been designed and synthesized. Palladium nanoparticles were uniformly ligated by CCPIL. After characterization, this composite has been applied as a heterogeneous catalyst for the Suzuki-Miyaura reaction of aryl halides with phenylboronic acid on water in the presence of NaOH as the base. These nanoparticles have also been applied for copper-free Sonogashira-Hagihara reaction in TBAB and Mizoroki-Heck reaction under solvent-free conditions. The catalyst was also found to be stable towards moisture and air and its catalytic activity remained almost unchanged after exposure to air for three months. This journal is the Partner Organisations 2014.
- Firouzabadi, Habib,Iranpoor, Nasser,Ghaderi, Arash,Gholinejad, Mohammad,Rahimi, Sajjad,Jokar, Safura
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p. 27674 - 27682
(2014/07/21)
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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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- Phosphine-free palladium-catalyzed decarboxylative coupling of alkynylcarboxylic acids with aryl and heteroaryl halides
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We herein report the design and development of a carboxyamido/carbene ligand and its Pd-complex for the decarboxylative coupling of alkynylcarboxylic acids with aryl and heteroaryl halides to afford arylalkynes. Copyright
- Reddy, Police Vishnuvardhan,Srinivas, Pottabathula,Annapurna, Manne,Bhargava, Suresh,Wagler, Jorg,Mirzadeh, Nedaossadat,Kantam, Mannepalli Lakshmi
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supporting information
p. 705 - 710
(2013/04/23)
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- Heck alkynylation (copper-free sonogashira coupling) of aryl and heteroaryl chlorides, using Pd complexes of t -Bu2(p -NMe2C 6H4)P: Understanding the structure-activity relationships and copper effects
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L2Pd(0) and L2Pd(II) complexes, where L= t-Bu 2(p-NMe2C6H4)P, have been identified as efficient catalyst systems for the Heck alkynylation of a variety of aryl bromides (17 examples) and aryl/heteroaryl chlorides (31 examples) with a range of aryl- and alkyl-acetylenes in excellent yields, under relatively low Pd loadings. The single-crystal X-ray structure determination of the presumably active catalytic species, L2Pd(0), was carried out in this study to better understand the superior activity of the current catalyst system from a structure-activity relationship point of view. The P-Pd-P bond angle indicates that the complex is bent (174.7) in comparison to the perfectly linear (180.0) structure of the analogous Pd(t-Bu3P)2. Preliminary mechanistic studies on the negative copper effect and substrate effect of aryl acetylenes were conducted to better understand the cross-coupling pathway of Heck alkynylation.
- Pu, Xiaotao,Li, Hongbo,Colacot, Thomas J.
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p. 568 - 581
(2013/03/13)
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- Transition-metal-free alkynylation of aryl chlorides
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Two sets of conditions have been developed for a base-mediated, transition-metal-free alkynylation of aryl chlorides that proceeds via benzyne intermediates. The first set of conditions involves the use of TMPLi base in a pentane/THF mixture at 25 °C. The
- Truong, Thanh,Daugulis, Olafs
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supporting information; experimental part
p. 4172 - 4175
(2011/10/02)
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- Regiochemistry in cobalt-mediated intermolecular Pauson-Khand reactions of unsymmetrical internal heteroaromatic alkynes with norbornene
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The intermolecular Pauson-Khand (PK) reactions of sterically comparable (2-phenylethynyl)heteroaromatic compounds with norbornene, mediated by Co 2(CO)8 to give cyclopentenone products, were examined in this study. A synthetic protocol utilizing focused-microwave dielectric heating proved indispensable in the efficient synthesis of the PK cyclopentenone products. "π-Deficient" heteroaromatic substrates, e.g., 2-pyrones, and some "π-excessive" heteroaromatics such as 2- and 3-thiophene and 2-furan favor the β-position in the newly formed cyclopentenone ring. Other π-excessive heteroaromatics such as 2-pyrrole or 2-indole favor the α-position. A π-excessive 3-indole derivative gave a nearly equal mixture of regioisomers. The position of the nitrogen in pyridyl-containing alkyne substrates also affects the regiochemical outcome of the PK reaction. A 2-pyridyl alkyne, possessing a proximal nitrogen, influences the regioselectivity relative to a 4-pyridyl variant quite dramatically, favoring the β-position in the newly formed cyclopentenone ring. A 2-pyrimidylalkyne exhibits similar behavior to the 2-pyridylalkyne. Compounds that do not participate in PK reactions with norbornene include (2-phenylethynyl)imidazoles and the related benzimidazoles, which promote rapid decomposition of the in situ generated (μ2-alkyne)Co2(CO)6 complexes. This stands in contrast with other nitrogen-containing heteroaromatics, e.g., pyrrole-, indole-, and pyrimidine-derived compounds, which effectively undergo PK reactions. Overall, the type of heteroaromatic group dramatically influences PK regioselectivity, which can in part be explained by rationalization of the current reaction mechanism, but not fully.
- Moulton, Benjamin E.,Whitwood, Adrian C.,Duhme-Klair, Anne K.,Lynam, Jason M.,Fairlamb, Ian J. S.
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experimental part
p. 5320 - 5334
(2011/08/06)
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- Hydrazone-promoted Sonogashira coupling reaction with aryl bromides at low palladium loadings
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The Sonogashira coupling reaction of aryl bromides with a variety of terminal alkynes in DMSO at 125 C gave internal arylated alkynes using low-loaded Pd(acac)with hydrazone as a ligand and CuI as the co-catalyst in good yields. Georg Thieme Verlag Stuttgart · New York.
- Mino, Takashi,Suzuki, Saori,Hirai, Kiminori,Sakamoto, Masami,Fujita, Tsutomu
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experimental part
p. 1277 - 1280
(2011/08/03)
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- Highly active and recyclable silica gel-supported palladium catalyst for mild cross-coupling reactions of unactivated heteroaryl chlorides
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Silica gel-supported β-ketoiminatophosphane-Pd complex (Pd@SiO 2) was shown to be a highly active and long-lived catalyst for aqueous Suzuki, Stille and Sonogashira coupling reactions of heteroaryl chlorides. A wide range of heteroaryl chlorides could be efficiently coupled with different nucleophilic partners in the presence of only 0.5 mol% catalyst and under mild conditions. This is one of the most powerful heterogeneous catalysts for the couplings of diverse heteroaryl chlorides. Furthermore, the catalyst could be reused with almost consistent activity. The Royal Society of Chemistry 2010.
- Lee, Dong-Hwan,Jung, Ji-Young,Jin, Myung-Jong
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experimental part
p. 2024 - 2029
(2011/02/22)
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- Sonogashira reaction of aryl and heteroaryl halides with terminal alkynes catalyzed by a highly efficient and recyclable nanosized MCM-41 anchored palladium bipyridyl complex
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A heterogeneous catalyst, nanosized MCM-41-Pd, was used to catalyze the Sonogashira coupling of aryl and heteroaryl halides with terminal alkynes in the presence of CuI and triphenylphosphine. The coupling products were obtained in high yields using low Pd loadings to 0.01 mol%, and the nanosized MCM-41-Pd catalyst was recovered by centrifugation of the reaction solution and re-used in further runs without significant loss of reactivity.
- Lin, Bo-Nan,Huang, Shao-Hsien,Wu, Wei-Yi,Mou, Chung-Yuan,Tsai, Fu-Yu
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experimental part
p. 9157 - 9173
(2011/02/27)
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- Synthesis of fused 4-Iodoselenophene[2,3-b]thiophenes by electrophilic cyclization of 3-alkynylthiophenes
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We present here our results on the electrophilic cyclization reaction of 3-alkynylthiophenes with different electrophiles such as I2, ICl, and PhSeBr. The cyclization reaction proceeded cleanly under mild reaction conditions, giving fused 4-iodoselenophene[2,3-b]thiophenes in excellent yields. In addition, the obtained chalcogenophenes were readily transformed into more complex products through palladium- or copper-catalyzed cross-coupling reactions with thiols, boronic acids, and organozinc reagents.
- Stein, Andre L.,Da Rocha, Juliana,Menezes, Paulo Henrique,Zeni, Gilson
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scheme or table
p. 705 - 710
(2010/03/24)
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- Sulfonated N-heterocyclic carbenes for Pd-catalyzed sonogashira and suzuki-miyaura coupling in aqueous solvents
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The reactions of the N, N-diarylimidazolium and N, N-diarylimidazolinium salts with chlorosulfonic acid result in the formation of the respective disulfonated N-heterocyclic carbene (NHC) precursors in reasonable yields (46-77%). Water-soluble palladium catalyst complexes, in situ obtained from the respective sulfonated imidazolinium salt, sodium tetrachloropalladate (Na 2PdCl4) and potassium hydroxide (KOH) in water, were successfully applied in the copper-free Sonogashira coupling reaction in isopropyl alcohol/water mixtures using 0.2 mol% catalyst loading. The preformed (disulfonatedNHC)PdCl(cinnamyl) complex was used in aqueous Suzuki-Miyaura reactions at 0.1 mol% catalyst loading. The coupling protocol reported here is very useful for Sonogashira reactions of N- and 5-heterocyclic aryl bromides and chlorides with aryl- and alkylacetylenes.
- Roy, Sutapa,Plenio, Herbert
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experimental part
p. 1014 - 1022
(2010/06/17)
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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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experimental part
p. 6293 - 6297
(2010/01/18)
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- Improved palladium-catalyzed sonogashira coupling reactions of aryl chlorides
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The improved palladium-catalyzed Sonogashira coupling reactions of aryl chlorides without the necessity to add copper salts were analyzed for the development of palladacycles, adamantylphosphines, carhene ligands, and 2-phosphino-N-arylin-doles and -pyrro
- Torborg, Christian,Huang, Jun,Schulz, Thomas,Schaeffner, Benjamin,Zapf, Alexander,Spannenberg, Anke,Borner, Armin,Beller, Matthias
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experimental part
p. 1329 - 1336
(2009/08/07)
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- A straightforward copper-free palladium methodology for the selective alkynylation of a wide variety of S-, O-, and N-based mono- and diheterocyclic bromides and chlorides
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High-yield alkynylations are successfully achieved by a simple and widely accessible catalytic system for an unprecedented variety of heterocyclic bromides and chlorides in position -2, -3 or -5: pyridine, quinoline, thiophene, furan, thiazole, benzothiazole, pyrimidine, pyridazine, pyrazine, dioxepin halides are efficiently functionalized in short time reactions. This copper-free methodology employs 1 mol % palladium only, with inexpensive PPh3 and amine base. The ionic liquid solvent allows a straigtforward separation of products and recycling opportunity. Unsuitable substrates and secondary reactions are also reported in order to point out further progress in cross-coupling using ionic liquids.
- Saleh, Samer,Picquet, Michel,Meunier, Philippe,Hierso, Jean-Cyrille
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experimental part
p. 7146 - 7150
(2009/12/06)
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- Copper-catalyzed three-component coupling of arynes, terminal alkynes and activated alkenes
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The three-component coupling of benzynes with terminal alkynes and activated alkenes in the presence of CuI, PCy3 and CsF in a 1: 1 mixture of CH3CN and THF at 50°C for 5 h gave 1-alkyl-2-alkynylbenzenes in good to moderate yields. The Royal Society of Chemistry.
- Bhuvaneswari, Sivakolundu,Jeganmohan, Masilamani,Cheng, Chien-Hong
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supporting information; experimental part
p. 5013 - 5015
(2009/06/05)
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