- Synthesis of magnetically recyclable Fe3O4@[(EtO)3Si–L1H]/Pd(II) nanocatalyst and application in Suzuki and Heck coupling reactions
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A Pd(II) Schiff base complex as an efficient and highly heterogeneous catalyst was developed by immobilization of a palladium complex on the surface of modified Fe3O4 magnetite nanoparticles. These surface-modified nanoparticles were characterized using various techniques such as transmission electron microscopy, X-ray diffraction, thermogravimetric analysis, vibrating sample magnetometry, elemental analysis and Fourier transform infrared spectroscopy. The palladium catalyst exhibited efficient catalytic activity in Suzuki and Heck coupling reactions. This method has notable advantages such as excellent chemoselectivity, mild reaction conditions, short reaction times and excellent yields. The yields of the products were in the range 85–100%. Also, the nanocatalyst can be easily recovered with a permanent magnet and reused at least five times without noticeable leaching or loss of its catalytic activity. Copyright
- Keypour, Hassan,Saremi, Shokoufeh Ghahri,Noroozi, Mohammad,Veisi, Hojat
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- New poly-imidazolium-triazole particles by CuAAC cross-linking of calix[4]arene bis-azide/alkyne amphiphiles - a prospective support for Pd in the Mizoroki-Heck reaction
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A new imidazolium amphiphilic calix[4]arene with terminal acetylene fragments in the polar region was synthesized according to a two step scheme including regioselective chloromethylation of distal di-O-butyl calix[4]arene and subsequent interaction with 1-(hex-5-yn-1-yl)-1H-imidazole. The aggregation properties (CAC, the size and zeta potential of aggregates) of alkynyl calix[4]arene as well as of previously synthesized azidopropyl calix[4]arene and their 1?:?1 mixture were disclosed. Macrocycles with azide and alkyne fragments in the polar region were covalently cross-linked under CuAAC conditions in water. Successful cross-linking of molecules has been proven by IR spectroscopy and MALDI-TOF spectrometry. The obtained polymeric particles were studied both in solution and the solid state and the presence of submicron (~200 nm) and micron (~1-5 μm) particles with the prevalence of the latter was found. The average molecular weight of the polymer according to the static light scattering data was found to be 639 ± 44 kDa. The obtained polymeric imidazolium-triazole particles were tested as a support for Pd(OAc)2in the Mizoroki-Heck reaction carried out in both organic and water media. In both solvents (especially in water) the addition of imidazolium-triazole particles to Pd(OAc)2increased the conversion of 4-iodanisole. It was found that the ratio between the products (1,1 and 1,2-substituted ethylenes) changes drastically on going from DMF to water from 1?:?5 to 1?:?40 when using supported Pd(OAc)2
- Burilov, Vladimir,Garipova, Ramilya,Mironova, Diana,Sultanova, Elza,Bogdanov, Ilshat,Ocherednyuk, Evgeny,Evtugyn, Vladimir,Osin, Yuri,Rizvanov, Ildar,Solovieva, Svetlana,Antipin, Igor
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- Continuous-flow Heck synthesis of 4-methoxybiphenyl and methyl 4-methoxycinnamate in supercritical carbon dioxide expanded solvent solutions
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The palladium metal catalysed Heck reaction of 4-iodoanisole with styrene or methyl acrylate has been studied in a continuous plug flow reactor (PFR) using supercritical carbon dioxide (scCO2) as the solvent, with THF and methanol as modifiers.
- Lau, Phei Li,Allen, Ray W. K.,Styring, Peter
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- Hydrogel supported vinylimidazole based PEPPSI-Pd-NHC catalysts: The catalytic activities in Heck and Suzuki-Miyaura coupling reactions
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Increasing environmental awareness and limited raw material resources have increased the importance of catalysts by leading to green technology. For this purpose, there is a need for efficient, new, selective, reusable, environmentally friendly catalysts
- Boztepe, Cihangir,Künkül, As?m,Gürbüz, Nevin
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- Stereoselective Base-Catalyzed 1,1-Silaboration of Terminal Alkynes
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A base-catalyzed reaction that enables stereoselective 1,1-silaboration of terminal alkynes is described. This method not only offers a new strategy to functionalize simple and readily accessible alkynes beyond 1,2-difunctionalization, but also provides a
- Gu, Yiting,Duan, Yaya,Shen, Yangyang,Martin, Ruben
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- PEG-modified N-heterocyclic carbene ligands for highly efficient and recyclable Pd-catalyzed Heck reaction in water
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A water-soluble and air-stable Pd(OAc)2/mPEG n MeImI system was found to be a highly efficient and reusable catalyst for the coupling of aryl halides and styrene in neat water using K2CO3 as base. After extraction, the catalytic system could be reused several times with only a slight decrease in its activity.
- Liu, Yulan,Wang, Yan,Long, Ensheng
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- New fragmentation and rearrangement reactions of the azetidine ring promoted by AlEt2Cl
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Azetidines 6 prepared by AlH2Cl reduction of easily available β-lactams 5 react with AlEt2Cl in CH2Cl2 solution at room temperature to yield, through new fragmentation or rearrangement reactions of the azetidine ring, either, olefins 7 or bicyclic fused pyrrolidines 8, depending on the nature of the group bonded to C2 of the four membered ring.
- Alcaide, Benito,Salgado, Nati R.,Sierra, Miguel A.
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- Synthesis, crystal structures, magnetic properties and Suzuki and Heck coupling catalytic activities of new coordination polymers containing tetracyanopalladate(II) anions
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Four novel coordination polymers, [Ni(bishydeten)Pd(CN)4] (1), [Cu(bishydeten)Pd(CN)4] (2), [Zn(bishydeten)Pd(CN)4] (3) and [Cd(bishydeten)Pd(CN)4] (4) (bishydeten = N,N′-bis(2- hydroxyethyl)ethylenediamine], have been synthesized and characterized by various techniques (elemental analysis, IR, EPR, X-ray and thermal analysis). In compound 4, all of the cyano groups use -N edges to form coordination bonds to Cd(II) in addition to -C atoms, resulting in the formation of a tridimensional network. The same situation is observed for compound 3 for one of the tetracyanopalladate(II) groups, while two cyano groups remain in the monodentate form coordinated to Pd(II) in the other tetracyanopalladate(II) group. While an EPR signal was not observed for 1, the g parameters obtained from the EPR spectrum of 2 indicated that the Cu(II) ions are located in tetragonal distorted octahedral sites (D4h) and that the ground state of the paramagnetic electron is dx2-y2. Variable temperature magnetic susceptibility measurements recorded in the range 15-300 K showed the presence of a very small antiferromagnetic interaction below 20 K for complexes 1 and 2. 2 was proven to be less effective as a catalyst than 1 under the Heck reaction conditions. Moreover, 1 was determined to be a more effective catalyst and more efficient for iodoarenes than bromoarenes under Suzuki coupling conditions.
- ?enocak, Ay?egül,Karada?, Ahmet,Yerli, Yusuf,Gürbüz, Nevin,?zdemir, Ismail,?ahin, Ertan
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- [60]Fullerene-Based Pd(0) Complexes of Phosphorus Ylides as Efficient Nanocatalyst for Homo- and Heterogeneous Mizoroki–Heck Coupling Reactions
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Abstract: This work reports the synthesis and catalytic properties of new mono- and bidentate palladium(0)-[60]fullerene complexes, prepared by reaction of α-keto stabilized phosphorus ylides [Ph2P(CH2)nPPh2=C(H)C(O)C6H4-p-R] (n = 1, R = Ph, NO2, (Y1, Y2); n = 2, R = Ph, NO2, (Y3, Y4)), C60 and Pd(dba)2 (dibenzylideneacetone (dba)). Two coordination modes were observed: bidentate P,C-coordinated in the case of [(η ?C60)Pd(κ2 ?Y1)] (1) and [(η2?C60)Pd(κ2?Y2)] (2) and monodentate P-coordinated for [(η2?C60)Pd(Y3)2] (3) and [(η2?C60)Pd(Y4)2] (4) complexes. All complexes have been fully characterized by 1H, 13C and 31P NMR spectroscopic methods and other conventional techniques such as IR, thermogravimetry, inductively coupled plasma optical emission spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy and transmission electron microscopy analysis. Also, the catalytic activity of [60]fullerene-based nanocatalyst 2 in homo- and heterogeneous Mizoroki–Heck coupling reactions of various aryl chlorides with styrene was evaluated. The results implied that the both reactions exhibit their beneficial aspects such as high activity for homogeneous catalysis and facile separation and reusability for heterogeneous one. Furthermore, DFT studies of geometry-optimized monodentate and bidentate structures for 1 and 3 were calculated at the BP86/LANL2DZ and B3LYP/LANL2MB levels of theory to understand the origin of the observed coordination modes. Graphical Abstract: [Figure not available: see fulltext.].
- Sabounchei, Seyyed Javad,Hashemi, Ali,Hosseinzadeh, Marjan,Salehzadeh, Sadegh,Maleki, Farahnaz
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- A macrocyclic Pd(II)-Ni(II) complex in Heck and Suzuki reactions
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A heterodinuclear Pd(II)-Ni(II) macrocyclic Schiff base complex was applied as a catalyst for Heck and Suzuki cross-coupling reactions. In reaction of 4-bromoanisole with styrene, 4-methoxy-trans-stilbene was formed as the main product with a yield of up to 87%. In the Suzuki coupling of 4-bromoanisole with PhB(OH)2in a 2-propanol/water solution, up to 96% of the product was obtained. Analyses of the post-reaction mixtures confirmed the high stability of the macrocyclic Pd(II)-Ni(II) complex under the reaction conditions. The partial decomposition of the complex started at the Ni(II) site.
- Mieczyńska, Ewa,Lisowski, Jerzy,Trzeciak, Anna M.
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- Preparation, optical properties and catalytic activity of TiO 2@Pd nanoparticles as heterogeneous and reusable catalysts for ligand-free Heck coupling reaction
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This paper reports the synthesis and use of TiO2@Pd nanoparticles, as reusable catalysts for Heck coupling reaction under ligand-free conditions. This method has the advantages of high yields, elimination of ligand and homogeneous catalysts, simple methodology and easy work up. Interestingly, the novel catalyst could be recovered in a facile manner from the reaction mixture and recycled several times without any significant loss in activity. The catalyst was characterized by SEM, EDS and UV-vis spectroscopy. Experimental absorbance spectra compared with results from the Mie theory.
- Nasrollahzadeh, Mahmoud,Azarian, Abbas,Ehsani, Ali,Khalaj, Mehdi
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- Development of Hierarchical Polymer@Pd Nanowire-Network: Synthesis and Application as Highly Active Recyclable Catalyst and Printable Conductive Ink
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A facile one-pot approach for preparing hierarchical nanowire-networks of hollow polymer@Pd nanospheres is reported. First, polymer@Pd hollow nanospheres were produced through metal-complexation-induced phase separation with functionalized graft copolymer
- Mir, Sajjad Husain,Ochiai, Bungo
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- New (NHC)Pd(II)(PPh3) complexes: synthesis, characterization, crystal structure and its application on Sonogashira and Mizoroki–Heck cross-coupling reactions
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In this study, new six Pd-based complexes containing mixture N-heterocyclic carbene (NHC) and triphenylphosphine (PPh3) ligands were synthesized from the reaction of the (NHC)PdI2(pyridine) with PPh3. The new (NHC)PdI
- Erdemir, Fato?,Akta?, Ayd?n,Barut Celepci, Duygu,G?k, Yetkin
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- Oxadiazoline and ketoimine palladium(II) complexes as highly efficient catalysts for Suzuki-Miyaura cross-coupling reactions in supercritical carbon dioxide
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The [2+3] cycloaddition of nitriles (RCN) with 2,2-dimethyl-3,4-dihydro-2H- pyrrole 1-oxide, in the presence of palladium dichloride (PdCl2) gives the corresponding 2,3-dihydro[1.2.4]oxadiazole (Δ4-1,2,4- oxadiazoline) palladium(II)
- Fernandes, Ricardo R.,Lasri, Jamal,DaSilva, M. Fatima C. Guedes,Palavra, Antonio M. F.,Dasilva, Jose A. L.,Dasilva, Joao J. R. Frausto,Pombeiro, Armando J. L.
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- Tetraalkylammonium-free heck olefination of deactivated chloroarenes by using a macrocyclic catalyst precursor
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Palladium reservoir: A macrocyclic dinuclear Pd complex is applied to the Heck coupling of strongly deactivated aryl chlorides. The complex serves as a very stable precatalyst, which releases active Pd under normal reaction conditions (see scheme). The co
- Roehlich, Christoph,Koehler, Klaus
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- Imidazole, pyrimidine and diazepine containing heteroaryl-substituted heterocyclic salts as efficient ligand precursors for Mizoroki-Heck coupling reaction: Synthesis, structural characterization and catalytic activities
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The nine new heteroaryl-substituted imidazolidinium (1a-c), pyrimidinium (2a-c) and diazepinium (3a-c) salts as N-heterocyclic carbene (NHC) precursors were synthesized in good yields and entirely characterized using elemental analyses and conventional sp
- G?k, Yetkin,Akko, Senem,Akkurt, Mehmet,Tahir, Muhammad Nawaz
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- Synthesis, characterization of N-heterocyclic carbene metallacrown palladium complex and catalytic activities in Suzuki and Heck coupling reaction
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A series of new N-heterocyclic carbene Metllacrown palladium complexes with a highly flexible polyether-bridged chain (CH2OCH2) n (n = 1-3) have been synthesized by the reaction of the corresponding silver complexes and PdCl2(CH3CN) 2 in acetonitrile. Complexes 7a,b-9a,b have been structurally characterized. A single-crystal X-ray study of palladium complex 1,1-(oxy-1,2-ethanediyl)bis[3-(1-naphthalenemethyl) imidazol-2-ylidene] palladium hexafluorophosphate 7a adopt a cis configuration. They exhibited excellent catalytic activity in Suzuki-Miyoura and Heck coupling of aryl bromide in the presence of KOH. Graphical abstract: A series of new N-heterocyclic carbene metallacrown palladium (II) complexes have been synthesized. These palladium complexes show excellent catalytic activity in Suzuki and Heck coupling reaction.[Figure not available: see fulltext.]
- Wang, Jun-Wen,Gao, Lin-Ying,Meng, Fan-Hui,Jiao, Jing,Ding, Ling-Yan,Zhang, Li-Fang
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- Palladium catalyzed Mizoroki-Heck and Suzuki-Miyaura reactions using naphthalenomethyl-substituted imidazolidin-2-ylidene ligands in aqueous media
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Naphthalenomethyl-substituted imidazolidinium salts (1a-g) were prepared and characterized by conventional spectroscopic methods, 1H NMR, 13C NMR, FTIR, and elemental analysis techniques. The in situ prepared three component systems naphthalenomethyl-substituted imidazolidinium salts, Pd(OAc)2, and K2CO3 catalyzed quantitatively the Mizoroki-Heck and Suzuki-Miyaura coupling of aryl halides under mild conditions in aqueous media.
- Aktas, Aydin,Akkoc, Senem,Goek, Yetkin
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- Palladium and Bimetallic Palladium-Nickel Nanoparticles Supported on Multiwalled Carbon Nanotubes: Application to Carbon-Carbon Bond-Forming Reactions in Water
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Palladium and bimetallic Pd-Ni nanoparticles (NPs) protected by polyvinylpyrrolidone were prepared by the reduction-by-solvent method and deposited on multiwalled carbon nanotubes (MWCNTs). The catalytic activity of these NPs to carbon-carbon bond-forming reactions was studied by using 0.1 mol% Pd loading, at 120°C for 1 h and water as a solvent under ligand-free conditions. The Suzuki-Miyaura reaction took place quantitatively for the cross-coupling of 4-bromoanisole with phenylboronic acid, better than those obtained with potassium phenyltrifluoroborate, with Pd50Ni50/MWCNTs as a catalyst and K2CO3 as a base and TBAB as an additive, with good recyclability during 4 cycles with some Ni leaching. The Hiyama reaction of 4-iodoanisole with trimethoxyphenylsilane, under fluoride-free conditions using 50% aqueous NaOH solution, was performed with Pd/MWCNTs as a catalyst in 83% yield with low recyclability. For the Mizoroki-Heck reaction 4-iodoanisole and styrene gave the corresponding 4-methoxystilbene quantitatively with Pd50Ni50/MWCNTs using K2CO3 as a base and TBAB as an additive although the recycle failed. In the case of the Sonogashira-Hagihara reaction, Pd/MWCNTs had to be used as a catalyst and pyrrolidine as a base for the coupling of 4-iodoanisole with phenylacetylene under copper-free conditions. The corresponding 4-methoxytolane was quantitatively obtained allowing the recycling of the catalyst during 3 cycles. From black to green: The catalytic activity of palladium and bimetallic Pd-Ni nanoparticles deposited on multiwalled carbon nanotubes as a catalyst for cross-coupling reactions in water under ligandless conditions is disclosed. These reaction conditions represent an environmentally friendly alternative to those previously reported for reactions in organic solvents.
- Ohtaka, Atsushi,Sansano, José M.,Nájera, Carmen,Miguel-García, Izaskun,Berenguer-Murcia, ángel,Cazorla-Amor?s, Diego
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- Kinetic investigation of a PC(sp3)P pincer palladium (II) complex in the Heck reaction
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An investigation of the kinetics of the Heck reaction between 4-iodoanisole and styrene catalysed by {cis-1,3-bis[(di-tert-butylphosphino)methyl]- cyclohexane} palladium (II) iodide (1) has been performed in DMF-d7 solution. Based on mercury po
- Nilsson, Patrik,Wendt, Ola F.
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- Synthesis and microwave-assisted catalytic activity of novel bis-benzimidazole salts bearing furfuryl and thenylmoieties in heck and suzuki cross-coupling reactions
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A mixture of bis-benzimidazole salts (1-7), Pd(OAc)2 and K 2CO3 in DMF - H2O catalyzes, in high yield, the Suzuki and Heck cross-coupling reactions assisted by microwave irradiation in a short time. In particular, the yields of the Heck and Suzuki reactionswith aryl bromideswere found to be nearly quantative. The synthesized bis-benzimidazole salts (1-7) were identified by 1H-13C NMR, IR spectroscopic methods and micro analysis. Copyright
- Yilmaz, Uelkue,Sireci, Nihat,Deniz, Selma,Kuecuekbay, Hasan
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- Picolyl substituted N-heterocyclic carbene/palladium catalyzed Heck reactions
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Novel 1,3-dialkylimidazolinium and 1,3-dialkyltetrahydropyrimidinium hexafluorophosphate salts as N-heterocyclic carbene precursors were prepared by reacting N, N'-dialkylethandiamine or N, N'-dialkylpropandiamine, triethyl orthoformate, and ammonium hexa
- Yigit, Beyhan,Yigit, Murat,Oezdemir, Ismail,Cetinkaya, Engin
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- Phosphine-Functionalized Chitosan Microparticles as Support Materials for Palladium Nanoparticles in Heck Reactions
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Herein, we investigated the activation and stabilization of Pd nanoparticles using microparticles of chitosan-functionalized with phosphine moieties. The catalytic activity of the prepared material was assessed in a series of Heck reactions, which demonst
- Biajoli, André F. P.,Fajardo, André R.,Lemos, Thalia S. A.,de Souza, Jaqueline F.
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- Palladium Nanoparticles Supported on Cellulosic Paper as Multifunctional Catalyst for Coupling and Hydrogenation Reactions
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Hallmark of a successful catalyst is its high efficiency, economic aspects, operational simplicity, extensive reusability, higher environment friendliness, and potential use in multiple industrial applications. Herein, a facile protocol involving a cataly
- Kalanthoden, Abdul Nasar,Zahir, Md. Hasan,Aziz, Md. Abdul,Al-Najar, Basmah,Rani, S. Kutti,Shaikh, M. Nasiruzzaman
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- Pd-Catalyzed Coupling of N-Tosylhydrazones with Benzylic Phosphates: Toward the Synthesis of Di- or Tri-Substituted Alkenes
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This study shows that various di- and tri-substituted alkenes with high chemoselectivity were obtained in good to high yields by coupling N-tosylhydrazones (NTHs) with benzylic phosphates as electrophilic partners. The obtained new catalytic system consis
- Zhang, Kena,Provot, Olivier,Alami, Mouad,Tran, Christine,Hamze, Abdallah
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p. 1249 - 1261
(2022/02/07)
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- Electrochemical Proton Reduction over Nickel Foam for Z-Stereoselective Semihydrogenation/deuteration of Functionalized Alkynes
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Selective reduction strategies based on abundant-metal catalysts are very important in the production of chemicals. In this paper, a method for the electrochemical semihydrogenation and semideuteration of alkynes to form Z-alkenes was developed, using a simple nickel foam as catalyst and H3O+ or D3O+ as sources of hydrogen or deuterium. Good yields and excellent stereoselectivities (Z/E up to 20 : 1) were obtained under very mild reaction conditions. The reaction proceeded with terminal and nonterminal alkynes, and also with alkynes containing easily reducible functional groups, such as carbonyl groups, as well as aryl chlorides, bromides, and even iodides. The nickel-foam electrocatalyst could be recycled up to 14 times without any change in its catalytic properties.
- Valiente, Alejandro,Martínez-Pardo, Pablo,Kaur, Gurpreet,Johansson, Magnus J.,Martín-Matute, Belén
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- Regio- and stereoselective synthesis of bromoalkenes by homolytic hydrobromination of alkynes with hydrogen bromide
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Homolytic hydrobromination of terminal and internal alkynes with a commercially available solution of hydrogen bromide in acetic acid has been investigated for regio- and stereoselective synthesis of bromoalkenes. Under an aerobic atmosphere at room temperature, the reaction of ethynylarenes with a small excess of HBr efficiently gave (2-bromoethenyl)arenes with good to high E-selectivity. (Alk-1-ynyl)arenes, or internal alkynes bearing both phenyl and alkyl groups at the sp-carbons also underwent the air-initiated hydrobromination to exhibit high Z-selectivity under kinetic conditions using a half equivalent of HBr.
- Kumaki, Wataru,Kinoshita, Hidenori,Miura, Katsukiyo
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- METHODS OF ARENE ALKENYLATION
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The present disclosure provides for a rhodium-catalyzed oxidative arene alkenylation from arenes and styrenes to prepare stilbene and stilbene derivatives. For example, the present disclosure provides for method of making arenes or substituted arenes, in particular stilbene and stilbene derivatives, from a reaction of an optionally substituted arene and/or optionally substituted styrene. The reaction includes a Rh catalyst or Rh pre-catalyst material and an oxidant, where the Rh catalyst or Rh catalyst formed Rh pre-catalyst material selectively functionalizes CH bond on the arene compound (e.g., benzene or substituted benzene).
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Page/Page column 18; 21-22; 42-43; 49
(2021/11/26)
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- Energy-Transfer-Mediated Photocatalysis by a Bioinspired Organic Perylenephotosensitizer HiBRCP
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Energy transfer plays a special role in photocatalysis by utilizing the potential energy of the excited state through indirect excitation, in which a photosensitizer determines the thermodynamic feasibility of the reaction. Bioinspired by the energy-transfer ability of natural product cercosporin, here we developed a green and highly efficient organic photosensitizer HiBRCP (hexaisobutyryl reduced cercosporin) through structural modification of cercosporin. After structural manipulation, its triplet energy was greatly improved, and then, it could markedly promote the efficient geometrical isomerization of alkenes from the E-isomer to the Z-isomer. Moreover, it was also effective for energy-transfer-mediated organometallic catalysis, which allowed realization of the cross-coupling of aryl bromides and carboxylic acids through efficient energy transfer from HiBRCP to nickel complexes. Thus, the study on the relationship between structural manipulation and their photophysical properties provided guidance for further modification of cercosporin, which could be applied to more meaningful and challenging energy-transfer reactions.
- Zhang, Yan,Xia, Mingze,Li, Min,Ping, Qian,Yuan, Zhenbo,Liu, Xuanzhong,Yin, Huimin,Huang, Shuping,Rao, Yijian
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p. 15284 - 15297
(2021/11/01)
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- Palladium Nanoparticles Anchored on Magnesium Organosilicate: An Effective and Selective Catalyst for the Heck Reaction
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A new and effective palladium catalyst supported on a magnesium organosilicate for application in the Heck reaction is presented. A group of compounds comprising 22 examples were synthesized in moderate to high yields (up to 99%) within a short time. The palladium supported on magnesium organosilicate catalyst was characterized as an amorphous solid by SEM, containing around 33% of palladium inside the solid, and even with this low quantity of palladium, the catalyst was very efficient in the Heck reaction. Besides, based on the Scherrer equation, the crystallite size of the synthesized palladium nanoparticles was ultrasmall (around 1.3 nm). This strategy is a simple and efficient route for the formation of C-C bonds via the Heck cross-coupling reaction.
- Dos Santos, Beatriz F.,Da Silva, Beatriz A. L.,De Oliveira, Aline R.,Sarragiotto, Maria H.,Rinaldi, Andrelson W.,Domingues, Nelson Luís C.
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supporting information
p. 1301 - 1306
(2020/11/04)
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- Pd supported on clicked cellulose-modified magnetite-graphene oxide nanocomposite for C-C coupling reactions in deep eutectic solvent
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Cellulose-modified magnetite-graphene oxide nanocomposite was prepared via click reaction and utilized for immobilization of palladium (Pd) nanoparticles without using additional reducing agent. The abundant OH groups of cellulose provided the uniform dispersion and high stability of Pd nanoparticles, while magnetite-graphene oxide as a supporting material offered high specific surface area and easy magnetic separation. The as-prepared nanocomposite served as a heterogeneous catalyst for the Heck and Sonogashira coupling reactions in various hydrophilic and hydrophobic deep eutectic solvents (DESs) as sustainable and environmentally benign reaction media. Among the fifteen DESs evaluated for coupling reactions, the hydrophilic DES composed of dimethyl ammonium chloride and glycerol exhibited the best results. Due to the low miscibility of catalyst and DES in organic solvents, the separated aqueous phase containing both of the catalyst and DES can be readily recovered by evaporating water and retrieved eight times with negligible loss of catalytic performance.
- Karimi, Sabah,Masteri-Farahani, Majid,Niakan, Mahsa,Shekaari, Hemayat
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- Recyclable heterogeneous iron supported on imidazolium ionic liquid catalysed palladium and copper-free Heck reaction
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A natural friendly iron-immobilized on imidazolium supported ionic liquid [Gmim]Cl-Fe (III) was effectively evaluated as a heterogeneous catalyst for Mizoroki-Heck reaction with good to excellent yield under solvent free condition. [Gmim]Cl-Fe (III) showed good activities that were comparable to that of palladium catalysts. Furthermore, this phosphine, copper and palladium- free catalyst was simply recovered from the reaction mixture and recycled seven times.
- Deepa, Manickam,Kalaivani, Kolanjinathan,Parasuraman, Karthikeyan,Selvarasu, Uthayanila
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- Bimetallic nano alloy architecture on a special polymer: Ni or Cu merged with Pd for the promotion of the Mizoroki–Heck reaction and the Suzuki–Miyaura coupling
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Abstract: Novel Ni-Pd and Cu-Pd bimetallic nano alloys was designed and heterogenized on the highly robust ABPBI [poly(2,5-benzimidazole)] polymer in high yields using NaBH4 as reducing agent. These were versatile ligand free catalysts for the Mizoroki–Heck reaction and Suzuki–Miyaura coupling. The bimetallic Ni-Pd-ABPBI catalyst for the Mizoroki–Heck reaction of 4-iodo anisole could be recycled 5 times with high yields. Aryl bromides could also be activated for the Mizoroki–Heck reaction using Cu-Pd-ABPBI NP catalysts, with moderate yields. Graphic abstract: Synopsis Novel bimetallic Ni-Pd and Cu-Pd nano alloys, heterogenized on the robust ABPBI [poly(2,5-benzimidazole)] polymer using NaBH4 as reducing agent, is described. These were versatile ligand free, noble metal conservative catalysts, for the Mizoroki–Heck reaction and the Suzuki–Miyaura coupling. Aryl bromides were activated for the Mizoroki–Heck reaction using the Cu-Pd-ABPBI catalyst.[Figure not available: see fulltext.]
- Patil, Vijay P,Kashid, Abhijit A,Solanki, Bhanupratap S,Kharul, Ulhas K,Iyer, Suresh
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- Immobilizing palladium on melamine-functionalized magnetic nanoparticles: An efficient and reusable phosphine-free catalyst for Mizoroki–Heck reaction
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A highly efficient and stable heterogeneous catalyst was successfully prepared by anchoring palladium(0) onto melamine-functionalized Fe3O4 magnetic nanoparticles (MNPs-Mel-Pd). With the aid of amine functional groups, melamine was covalently bonded on epoxy functionalized magnetic nanoparticles and then Pd(0) was immobilized on this support with high dispersion. The prepared nanocatalyst exhibits excellent catalytic activity for C-C cross coupling (Mizoroki–Heck) of various aryl halides (iodide, bromides, and chrlorides) with olefins under mild reaction condition in relatively short reaction times. The synthesized nanocatalyst was characterized using Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), vibrating sample magnetometer (VSM), and X-ray photoelectron spectroscopy (XPS) techniques. The loading level of Pd in MNPs-Mel-Pd catalyst was measured to be 1.26 × 10?3 mol g?1 by atomic absorption spectroscopy (AAS). In addition, the catalyst can be easily separated and recovered from the reaction mixture by using an external magnet. The heterogeneity of the catalyst was confirmed by the hot filtration test, which was reused for at least six times under the optimized conditions without any significant loss of its activity.
- Aryanasab, Fezzeh,Shabanian, Meisam,Laoutid, Fouad,Vahabi, Henri
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- Water-Sculpting of a Heterogeneous Nanoparticle Precatalyst for Mizoroki-Heck Couplings under Aqueous Micellar Catalysis Conditions
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Powdery, spherical nanoparticles (NPs) containing ppm levels of palladium ligated by t-Bu3P, derived from FeCl3, upon simple exposure to water undergo a remarkable alteration in their morphology leading to nanorods that catalyze Mizoroki-Heck (MH) couplings. Such NP alteration is general, shown to occur with three unrelated phosphine ligand-containing NPs. Each catalyst has been studied using X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), and cryogenic transmission electron microscopy (cryo-TEM) analyses. Couplings that rely specifically on NPs containing t-Bu3P-ligated Pd occur under aqueous micellar catalysis conditions between room temperature and 45 °C, and show broad substrate scope. Other key features associated with this new technology include low residual Pd in the product, recycling of the aqueous reaction medium, and an associated low E Factor. Synthesis of the precursor to galipinine, a member of the Hancock family of alkaloids, is suggestive of potential industrial applications.
- Pang, Haobo,Hu, Yuting,Yu, Julie,Gallou, Fabrice,Lipshutz, Bruce H.
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supporting information
p. 3373 - 3382
(2021/04/07)
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- Efficient photocatalytic chemoselective and stereoselective C-C bond formation over AuPd@N-rich carbon nitride
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Heterogeneous chemoselective or stereoselective C-C coupling reactions remain extremely challenging in traditional organic synthesis. Here, we constructed a AuPd@N-rich carbon nitride (NRCN) photocatalyst through simple ammonia solution heat treatment of carbon nitride and then AuPd NP loading. AuPd@NRCN exhibited extraordinary light color promoted catalytic performance in C-C bond formation under visible light in air. Surprisingly, both high chemoselectivity to unsymmetrical Ullmann biaryl products and satisfactory stereoselectivity to Z-type Heck reaction products could be achieved by changing the light source color. Various substrates exhibited great potential for the economical synthesis of unsymmetrical biaryl products and Z-type olefins. Efficient visible light promoted C-I bond activation accompanied with improved photocatalytic coupling reaction efficiency over AuPd@NRCN was verified firstly by in situ DRIFTS. Considering that the Ullmann cross-coupling reaction is a multi-photon reaction, the improved photocatalytic performance in the Ullmann cross-coupling reaction using a combination of light sources with different colors might be due to the activation of different substrates and/or steps requiring different energies, and the combination of the two energy sources was beneficial for improving the activation efficiency of different substrates and/or steps. The activation of iodobenzene and styrene in the Heck reaction with light was also beneficial to the formation of the stilbene product. The light color promoted chemoselectivity and stereoselectivity are expected to have profound impact on organic synthetic methodology improvement. This journal is
- Jiang, Heyan,Xu, Jie,Zhang, Sishi,Cheng, Hongmei,Zang, Cuicui,Bian, Fengxia
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p. 219 - 229
(2021/01/28)
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- Synthesis, crystal structure, and catalytic activity of bridged-bis(N-heterocyclic carbene) palladium(II) complexes in selective Mizoroki-Heck cross-coupling reactions
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A series of three 1,3-propanediyl bridged bis(N-heterocyclic carbene)palladium(II) complexes (Pd-BNH1, Pd-BNH2, and Pd-BNH3), with + I effect order of the N-substituents of the ligand (isopropyl > benzyl > methoxyphenyl), was the subject of a spectroscopic, structural, computational and catalytic investigation. The bis(NHC)PdBr2 complexes were evaluated in Mizoroki-Heck coupling reactions of aryl bromides with styrene or acrylate derivatives and showed high catalytic efficiency to produce diarylethenes and cinnamic acid derivatives. The X-ray structure of the most active palladium complex Pd-BNH3 shows that the Pd(II) center is bonded to the two carbon atoms of the bis(N-heterocyclic carbene) and two bromide ligands in cis position, resulting in a distorted square planar geometry. The NMR data of Pd-BNH3 are consistent with a single chair-boat rigid conformer in solution with no dynamic behavior of the 8-membered ring palladacycle in the temperature range 25–120 °C. The catalytic activities of three Pd-bridged bis(NHC) complexes in the Mizoroki-Heck cross-coupling reactions were not found to have a direct correlation with +I effect order of the N-substituents of the ligand. However, a direct correlation was found between the DFT calculated absolute softness of the three complexes with their respective catalytic activity. The highest calculated softness, in the case of Pd-BNH3, is expected to favor the coordination steps of both the soft aryl bromides and alkenes in the Heck catalytic cycle.
- El Ali, Bassam,Fettouhi, Mohammed,Iali, Wissam,Mansour, Waseem,Suleiman, Rami
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- Synthesis of N-Heterocyclic Carbine Silver(I) and Palladium(II) Complexes with Acylated Piperazine Linker and Catalytic Activity in Three Types of C—C Coupling Reactions
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Two bis-imidazolium salts LH2·Cl2 and LH2·(PF6)2 with acylated piperazine linker and two N-heterocyclic carbene (NHC) silver(I) and palladium(II) complexes [L2Ag2](PF6)2 (1) and [L2Pd2Cl4] (2) were prepared. The crystal structures of LH2·Cl2 and 1 were confirmed by X-ray analysis. In 1, one 26-membered macrometallocycle was generated through two silver(I) ions and two bidentate ligands L. The catalytic activity of 2 was investigated in Sonogashira, Heck-Mizoroki and Suzuki-Miyaura reactions. The results displayed that these C—C coupling reactions can be smoothly carried out under the catalysis of 2.
- Liu, Qingxiang,Zhang, Xiantao,Zhao, Zhixiang,Li, Xinying,Zhang, Wei
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supporting information
p. 605 - 613
(2021/02/01)
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- Palladium supported aminobenzamide modified silica coated superparamagnetic iron oxide as an applicable nanocatalyst for Heck cross-coupling reaction
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An applicable palladium-based nanocatalyst was constructed through the immobilization of palladium onto 2-aminobenzamide functionalized silica coated superparamagnetic iron oxide magnetic nanoparticles. The nanocatalyst (named as Pd@ABA@SPIONs@SiO2) was characterized by several characterization methods, including scanning electron microscope (SEM), transmission electron microscopy (TEM), vibrating-sample magnetometry (VSM), energy-dispersive X-ray spectroscopy (EDS), dynamic light scattering (DLS), X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), inductively coupled plasma (ICP), and X-ray photoelectron spectroscopy (XPS) analyses. Microscopy results showed that the nanoparticles are spherical in shape with 20–25 nm size. The size of the nanoparticles was confirmed by the DLS method. The superparamagnetic nature of the catalyst was confirmed by the VSM method. The successful functionalization of SPIONs@SiO2 was confirmed by FT-IR spectroscopy. The presence of palladium in the structure of the nanocatalyst was illustrated by XRD and EDS analysis. Also using XPS technique, the oxidation state of palladium in Pd@ABA@SPIONs@SiO2 was determined zero before and after the catalyst was applied in Mizoroki-Heck reaction. Several aryl halides and alkenes were reacted in the presence of the nanocatalyst and formed the corresponding products in high isolated yields. The nanocatalyst showed very good reusability and did not decrease its activity after 10 sequential runs. Density functional theory (DFT) calculation was performed to provide a mechanism for the reaction and confirmed the role of the palladium catalyst in the reaction function.
- Fatahi, Yousef,Ghaempanah, Aram,Ma?mani, Leila,Mahdavi, Mohammad,Bahadorikhalili, Saeed
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- Introduction of a Recyclable Basic Ionic Solvent with Bis-(NHC) Ligand Property and The Possibility of Immobilization on Magnetite for Ligand- and Base-Free Pd-Catalyzed Heck, Suzuki and Sonogashira Cross-Coupling Reactions in Water
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A new versatile and recyclable NHC ligand precursor has been developed with ligand, base, and solvent functionalities for the efficient Pd-catalyzed Heck, Suzuki and Sonogashira cross-coupling reactions under mild conditions. Furthermore, NHC ligand precursor was immobilized on magnetite and its catalytic activity was also evaluated towards the coupling reactions as a heterogeneous catalyst. The NHC ligand precursor was prepared with imidazolium functionalization of TCT followed by a simple ion exchange by hydroxide ions. However, the results revealed an excellent catalytic activity for the both homogeneous and heterogeneous catalytic systems. 1.52?g.cm?3 and 1194 cP was obtained for the density and viscosity of the NHC ligand precursor respectively. On the other hand, the heterogeneous type could be readily recovered from the reaction mixture and reused for several times while preserving its properties. Heterogeneous nature of the magnetic catalyst was studied by hot filtration, mercury poisoning, and three-phase tests. High to excellent yields were obtained for all entries for the both homogeneous and heterogeneous catalysts, which reflects the high consistency of the catalyst. Graphic Abstract: [Figure not available: see fulltext.]
- Min, Qingwang,Miao, Penghua,Chu, Deyu,Liu, Jinghan,Qi, Meijuan,Kazemnejadi, Milad
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p. 3030 - 3047
(2021/02/16)
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- Immobilized Pd on a NHC-functionalized metal-organic FrameworkMIL-101(Cr): An efficient heterogeneous catalyst in the heck and copper-free Sonogashira coupling reactions
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A heterogeneous palladium catalyst system based on immobilization of palladium moieties on a N-heterocyclic carbene (NHC) modified metal organic framework (MOF) was developed for the Heck and copper-free Sonogashira coupling reactions. In order to prepare this catalyst system, first, MIL-101(Cr) was functionalized with NHC moieties through a post synthetic modification (PSM) approach, and then Pd metal was stabilized on the prepered MIL-101(Cr)-NHC substrate. This material was characterized using various microscopic and spectroscopic techniques and then was used as an efficient heterogeneous Pd catalyst system in the Heck and copper-free Sonogashira reactions. Results of the heterogeneity tests showed that the Pd-NHC-MIL-101(Cr) catalyst can efficiently catalyzed these coupling reactions heterogeneously and no remarkable changes observed in the morphology and structure of MIL-101(Cr) template during the reaction progress. Also, existence of palladium nanoparticles immobilized on the MOF structure affirmed by the TEM and XPS analysis confirmed the oxidation state of Pd. A variety of alkene and alkyne derivatives were synthesized in good to excellent yields using this heterogeneous Pd catalyst system under normal conditions. More importantly Pd-NHC-MIL-101(Cr) catalyst was simply recovered from the reaction medium without remarkable decreasing in its catalytic activities after five times of reusability. The ICP analysis showed the very low Pd and Cr metals leaching, representing high stability and applicability of this catalyst in Pd coupling reactions.
- Niknam, Esmaeil,Panahi, Farhad,Khalafi-Nezhad, Ali
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supporting information
(2021/01/12)
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- Green and sustainable palladium nanomagnetic catalyst stabilized by glucosamine-functionalized Fe3O4@SiO2 nanoparticles for Suzuki and Heck reactions
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A novel magnetic and heterogeneous palladium-based catalyst stabilized by glucosamine-functionalized magnetic Fe3O4@SiO2 nanoparticle was synthesized. The strategy relies on the covalently bonding of glucosamine to cyanuric chloride-functionalized magnetic nanoparticles followed by complexation with palladium. The structure of magnetic nanocatalyst was fully determined by FT-IR, XRD, DLS, FE-SEM, TEM, ICP, UV-Vis, TGA, VSM, and EDX. The obtained results confirmed that the palladium nanoparticles stabilized by glucosamine immobilized onto the magnetic support exhibited high activity in cross-coupling reactions of Suzuki-Miyaura and Mizoroki-Heck. Various aryl halides were coupled with arylboronic acid (Suzuki cross-coupling reaction) and olefins (Heck reactions) under the green conditions to provide corresponding products in high to excellent yields. Interestingly, the catalyst can be easily isolated from the reaction media by magnetic decantation and can subsequently be applied for consecutive reaction cycles (at least seven times) with no notable reduction in the catalytic activity.
- Eslahi, Hassan,Sardarian, Ali Reza,Esmaeilpour, Mohsen
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- Palladium Complexes with Phenoxy- And Amidate-Functionalized N-Heterocyclic Carbene Ligands Based on 3-Phenylimidazo[1,5- a]pyridine: Synthesis and Catalytic Application in Mizoroki-Heck Coupling Reactions with Ortho-Substituted Aryl Chlorides
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Mononuclear and tetranuclear palladium complexes with functionalized "abnormal"N-heterocyclic carbene (aNHC) ligands based on 3-phenylimidazo[1,5-a]pyridine were synthesized. All of the new complexes were structurally characterized by single-crystal X-ray diffraction studies. The new complexes were applied in the Mizoroki-Heck coupling reaction of aryl chlorides with alkenes in neat n-tetrabutylammonium bromide (TBAB). The mononuclear palladium complex with a tridentate phenoxy- and amidate-functionalized aNHC ligand displayed activity superior to that of the palladium complex with a bidentate amidate-functionalized aNHC ligand. The new tetranuclear complex with the tridentate ligand displayed the best activities, capable of the activation of deactivated aryl chlorides as substrates with a low Pd atom loading. Even challenging sterically demanding ortho-substituted aryl chlorides were successfully utilized as substrates. The studies revealed that the robustness of the catalyst precursor is crucial in delivering high catalytic activities. Also, the promising use of tetranuclear palladium complexes with functionalized aNHC ligands as the catalyst precursors in the Mizoroki-Heck coupling reaction in neat TBAB was demonstrated.
- Hung, Cheng-Hau,Zheng, Wei-Yuan,Lee, Hon Man
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p. 702 - 713
(2021/04/02)
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- N-Heterocyclic carbene palladium (II)-pyridine (NHC-Pd (II)-Py) complex catalyzed heck reactions
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A mild, efficient, and practical catalytic system for the synthesis of highly privileged stilbene pharmacophores is reported. This system uses N-heterocyclic carbene palladium (II) Pyridine (NHC-Pd (II)-Py) complex to catalyze the formation of carbon-carbon bonds between olefin derivatives and various bromide. This simple, gentle and user-friendly method can offer a variety of stilbene products in excellent yields under solvent-free condition. And its scale-up reaction has excellent yield and this system can be applied to industrial fields. The utility of this method is highlighted by its universality and modular synthesis of a series of bioactive molecules or important medical intermediates.
- Li, Dan,Tian, Qingqiang,Wang, Xuetong,Wang, Qiang,Wang, Yin,Liao, Siwei,Xu, Ping,Huang, Xin,Yuan, Jianyong
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supporting information
p. 2041 - 2052
(2021/05/25)
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- Palladium Loaded Dendronized Polymer as Efficient Polymeric Sustainable Catalyst for Heck Coupling Reaction
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The palladium incorporated amine-functionalized dendronized polymer was synthesized by the addition of palladium acetate to dendronized polymer in methanol at room temperature. Palladium species are immobilized onto the dendritic structure by their coordination with amino functional groups. The newly developed dendritic system showed high palladium content in the low generation level itself, which was found to be 4.19?mmol/g. This was fairly higher than, the other palladium-based catalysts. Energy dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, UV–Visible spectroscopy, and X-ray photoelectron spectroscopy were used to confirm the successful synthesis of the new catalyst. It was used as a homogeneous palladium catalyst for Heck coupling reaction between olefins and differently substituted aryl halides and the products were isolated in high yield. The products isolated were in trans configuration, which indicated the selectivity of the newly developed catalytic system. Also, this catalyst system was reused up to nine times without a significant decrease in its catalytic activity. The easy accessibility of catalytic sites, stability, resistance to metal leaching, high catalytic activity and remarkable stereoselectivity with a low amount of catalyst are all due to the dendritic support. The docking study was carried out for all the stilbene derivatives obtained by the Heck coupling reaction against DprE1 protein to study its potential antitubercular activity. All the compounds displayed superior docking score values over the range ??6.5 to ??8.2?kcal/mol, compared to the standard drug isoniazid with docking score of ??6.1?kcal/mol against DprE1. Graphic Abstract: [Figure not available: see fulltext.]
- Hiba, K.,Krishna, G. Anjali,Prathapan, S.,Sreekumar, K.
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- Transition-Metal-Free Matsuda-Heck Type Cross-Coupling and Mechanistic Evidence for a Radical Mechanism
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The Matsuda-Heck reaction, usually performed with palladium catalysts, can be carried out under transition-metal-free conditions in the presence of a KOtBu/DMF couple. This system allows the selective and direct synthesis of stilbenes from aryldiazonium salts under mild temperature (20 °C). Mechanistic studies suggest a radical pathway in which the DMF acts as the initiator of the overall process.
- Bergès, Julien,Zaid, Yassir,Tlili, Anis,Sotiropoulos, Jean-Marc,Taillefer, Marc
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supporting information
p. 1559 - 1563
(2021/02/27)
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- Ligand-Free Palladium-Catalyzed Carbonylative Suzuki Couplings of Vinyl Iodides with Arylboronic Acids under Substoichiometric Base Conditions
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A ligand-free palladium-catalyzed carbonylation of vinyl iodides with arylboronic acids, permitting the synthesis of chalcones and α-branched enones, has been established. This reaction proceeds smoothly at ambient pressure and temperature, and works well even with a substoichiometric amount of base. Importantly, this mild, efficient, and operationally simple protocol is suitable for the late-stage functionalization of an epiandrosterone-derived complex molecule.
- Yang, Zhiyuan,Gong, Pei-Xue,Chen, Junjie,Zhang, Jie,Gong, Xu,Han, Wei
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supporting information
p. 1207 - 1212
(2021/06/18)
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- Ligand-Free Catalytic Cross-Coupling in the System Aryl Halide–Arylacetylene–Alkene
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Abstract: Three-component cross-coupling in the system aryl halide–arylacetylene–alkenein the presence of simplest ligand-free palladium catalysts gave products ofboth 1+1+1-coupling and cross-dimerization of arylacetylene with alkene. Thepossibility of c
- Lagoda,Vidyaeva,Larina,Kurokhtina,Schmidt
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- NiFe2O4@SiO2@ZrO2/SO42-/Cu/Co nanoparticles: A novel, efficient, magnetically recyclable and bimetallic catalyst for Pd-free Suzuki, Heck and C-N cross-coupling reactions in aqueous media
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The novel heterogeneous bimetallic nanoparticles of Cu-Co were synthesized based on magnetic nanoparticles, and the magnetic nanocatalyst was characterized by XRD, FE-SEM, EDX mapping, BET, TEM, HRTEM, FTIR, TGA, and VSM. This catalyst was successfully applied as a recyclable magnetically catalyst in Heck, Suzuki, and C-N cross-coupling reactions with various aryl halides (iodides, bromides, and chlorides as challengeable substrates), with olefins, phenylboronic acid, and amines, respectively. We considered the rise of synergetic effects from the different Lewis acid and Br?nsted acid sites present in the catalyst. The catalyst was synthesized with cheap, available materials and a simple synthesis method. The catalyst can be separated easily using an external magnet. It was recycled for more than ten runs without a sensible loss of its catalytic activity, and no significant leaching of the Cu and Co quantity was observed. The significant benefits of the method are high-level generality, simple operation, and there are no heavy metals and toxic solvents. This is a quick, easy, efficacious and environmentally friendly protocol, and no by-products are formed in the reaction. These features make it an appropriate practical alternative protocol. In comparison with recent works, the other advantage of this catalyst is the synthesis of a wide variety of C-C and C-N bond derivatives (more than 40 derivatives). The other significant advantage is the low temperature of the reaction and the use of the least possible amount of the catalyst (0.003 g). The efficiency was good to excellent and the catalyst selectivity has been high. We aspire that our study inspires more interest to design novel catalysts based on using low-cost metal ions (such as cobalt and copper) in the cross-coupling reactions. This journal is
- Alavi G., Seyyedeh Ameneh,Nasseri, Mohammad Ali,Kazemnejadi, Milad,Allahresani, Ali,Hussainzadeh, Mahdi
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p. 7741 - 7757
(2021/05/13)
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- Mesoporous silica nanospheres supported atomically precise palladium nanocluster: Highly efficient and recyclable catalysts in the reduction of 4-nitrophenol and Heck reactions
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Atomically precise palladium nanoclusters show great potential applications in the field of catalysis owing to its ultrasmall size and precise structure. This work, we report the mesoporous silica nanoparticles (MSNs) supported [Pd3Cl(PPh3)3(PPh2)2]Cl catalysts (denoted as Pd3Cl/MSNs) for the reduction of 4-nitrophenol and Heck coupling reactions of iodobenzene and styrenes. High uniform MSNs, with average diameter ≈110 nm, were prepared by sol–gel method, followed by Pd nanoclusters immobilization into the pore of MSNs. The MSNs supported Pd nanoclusters were well characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR), and diffuse reflectance optical spectrum. The results indicated that Pd3Cl nanoclusters after immobilized into the pores of MSNs are intact and possess good dispersibility. The catalytic performance of as-prepared nanocomposites was evaluated by the reduction of 4-nitrophenol and Heck reactions. The 4-nitrophenol could be completely conversion to 4-aminophenol within 6?min. Meanwhile, the as-prepared Pd3Cl/MSNs exhibit excellent catalytic performance in the Heck reactions between iodobenzenes and styrenes. The high catalytic activity of Pd3Cl/MSNs could be attributed to the large surface area and unique geometric structure of as-prepared Pd nanoclusters. More importantly, the catalysts could be easily recycled by centrifugation and shows excellent reusability.
- Gao, Taiping,Kang, Zhenlu,Zhao, Yining,Zhou, Yilin
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- Pd salen complex@CPGO as a convenient, effective heterogeneous catalyst for Suzuki–Miyaura and Heck–Mizoroki cross-coupling reactions
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A Pd(II) Schiff base complex supported on graphene oxide nanosheets (Pd(II) salen@CPGO) has been synthesized and characterized by FT-IR, ICP-AES, XRD, SEM/EDX and TEM. The synthesized nanocatalyst has been found to be an efficient heterogeneous catalyst for Suzuki–Miyaura and Heck–Mizoroki coupling reactions. Pd(II) salen@CPGO could be separated and recovered easily from the reaction mixture and recycled several times without a discernible decrease in its catalytic activity. The construction of a solid sheet-supported Pd catalyst would be expected to be a promising system to perform heterogeneous catalytic reactions.
- Ghabdian, Mahdieh,Nasseri, Mohammad Ali,Allahresani, Ali,Motavallizadehkakhky, Alireza
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p. 1713 - 1728
(2018/05/25)
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- New Nickel-Based Catalytic System with Pincer Pyrrole-Functionalized N-Heterocyclic Carbene as Ligand for Suzuki-Miyaura Cross-Coupling Reactions
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A new catalytic system with Ni(NO3)2·6H2O as the catalyst and a pincer pyrrole-functionalized N-heterocyclic carbene as the ligand was employed in the Suzuki-Miyaura cross-coupling reactions of aryl iodides with arylboronic acids. With 5 mol% catalyst, the catalytic reactions proceeded at 160 °C, giving coupling products in isolated yields of up to 94% in short reaction times (1-4 h). The system worked efficiently with aryl iodides bearing electron-donating or electron-withdrawing groups and arylboronic acids with electron-donating groups. Steric effects were observed for both aryl iodides and arylboronic acids. It is proposed that the reactions underwent a Ni(I)/Ni(III) catalytic cycle.
- Guo, Zhifo,Lei, Xiangyang
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supporting information
(2021/09/11)
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- Dinuclear cobalt complex-catalyzed stereodivergent semireduction of alkynes: Switchable selectivities controlled by H2O
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Catalytic semireduction of internal alkynes to alkenes is very important for organic synthesis. Although great success has been achieved in this area, switchable Z/E stereoselectivity based on a single catalyst for the semireduction of internal alkynes is a longstanding challenge due to the multichemo- and stereoselectivity, especially based on less-expensive earth-abundant metals. Herein, we describe a switchable semireduction of alkynes to (Z)- or (E)-alkenes catalyzed by a dinuclear cobalt complex supported by a macrocyclic bis pyridyl diimine (PDI) ligand. It was found that cis-reduction of the alkyne occurs first and the Z-E alkene stereoisomerization process is formally controlled by the amount of H2O, since the concentration of H2O may influence the catalytic activity of the catalyst for isomerization. Therefore, this protocol provides a facile way to switch to either the (Z)- or (E)-olefin isomer in a single transformation by adjusting the amount of water.
- Chen, Ke,Zhu, Hongdan,Li, Yuling,Peng, Qian,Guo, Yinlong,Wang, Xiaoming
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p. 13696 - 13705
(2021/11/16)
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- Ruthenium-Catalyzed E-Selective Partial Hydrogenation of Alkynes under Transfer-Hydrogenation Conditions using Paraformaldehyde as Hydrogen Source
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E-alkenes were synthesized with up to 100 % E/Z selectivity via ruthenium-catalyzed partial hydrogenation of different aliphatic and aromatic alkynes under transfer-hydrogenation conditions. Paraformaldehyde as a safe, cheap and easily available solid hydrogen carrier was used for the first time as hydrogen source in the presence of water for transfer-hydrogenation of alkynes. Optimization reactions showed the best results for the commercially available binuclear [Ru(p-cymene)Cl2]2 complex as pre-catalyst in combination with 2,2-bis(diphenylphosphino)-1,1-binaphthyl (BINAP) as ligand (1 : 1 ratio per Ru monomer to ligand). Mechanistic investigations showed that the origin of E-selectivity in this reaction is the fast Z to E isomerization of the formed alkenes. Mild reaction conditions plus the use of cheap, easily available and safe materials as well as simple setup and inexpensive catalyst turn this protocol into a feasible and promising stereo complementary procedure to the well-known Z-selective Lindlar reduction in late-stage syntheses. This procedure can also be used for the production of deuterated alkenes simply using d2-paraformaldehyde and D2O mixtures.
- Fetzer, Marcus N. A.,Tavakoli, Ghazal,Klein, Axel,Prechtl, Martin H. G.
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p. 1317 - 1325
(2021/02/11)
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- PVC-NHC-Pd(0): An efficient and reusable heterogeneous catalyst for highly cis-selective semihydrogenation of alkynes using formic acid as hydrogen source
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PVC-NHC-Pd(0) catalyst was prepared and exerted to highly cis-selective semihydrogenation of diarylacetylene using formic acid as hydrogen source under mild condition. The as-prepared catalyst was well characterized by various techniques such as FT-IR, 1H NMR, XRD, SEM, EDX, TEM, XPS, and TGA. The catalyst can be easily recovered and recycled without loss of its activity and selectivity owing to the metal-ligand interaction between Pd(0) with polymeric NHC ligands. This protocol is an attractive alternative of the classical Lindlar's hydrogenation.
- Li, Yiqun,Zheng, Waner,Zhou, Yuemin
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- Bimetallic Ni–Pd Synergism—Mixed Metal Catalysis of the Mizoroki-Heck Reaction and the Suzuki–Miyaura Coupling of Aryl Bromides
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Abstract: A combination of Pd and Ni complexes activated aryl bromides for the thermal Mizoroki-Heck reaction and Suzuki coupling giving high yields in short reaction times. A thermal redox mechanism probably occurs whereby Ni complex transfers electron and reduces the Pd (II) to Pd (0) which then takes the reactants through the standard protocol of oxidative-addition, migratory insertion and reductive elimination, typical for the Mizoroki-Heck reaction and the Suzuki coupling. Graphic Abstract: [Figure not available: see fulltext.]
- Kashid, Abhijit A.,Patil, Dharmaraj J.,Mali, Ramling D.,Patil, Vijay P.,Neethu,Meroliya, Heena K.,Waghmode, Shobha A.,Iyer, Suresh
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p. 353 - 358
(2020/08/05)
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- Stereospecific Iron-Catalyzed Carbon (sp2)-Carbon (sp2) Cross-Coupling of Aryllithium with Vinyl Halides
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We present herein an efficient synthetic protocol involving iron-catalyzed cross-coupling of organolithium compounds with vinyl halides as key coupling partners. More than 30 examples were obtained with moderate to good yields and high stereoselectivities. The practicality of this method is evidenced by a gram-scale synthesis. In addition, a preliminary mechanistic investigation was also performed.
- Chen, Peng,Peng, Xiao-Shui,Wang, Zhi-Yong,Wong, Henry N. C.
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supporting information
p. 4385 - 4390
(2021/06/27)
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- Illuminating Stannylation
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We have developed photoboosted stannylation reactions of terminal alkynes (linear-selective hydrostannylation) and fluoroarenes (defluorostannylation), in which the stannyl anion is photoexcited to an excited triplet (T1) stannyl diradical species. This u
- Sakamoto, Kyoka,Nagashima, Yuki,Wang, Chao,Miyamoto, Kazunori,Tanaka, Ken,Uchiyama, Masanobu
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p. 5629 - 5635
(2021/05/04)
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- Wittig Olefination Using Phosphonium Ion-Pair Reagents Incorporating an Endogenous Base
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Despite common perception, the use of strong bases in Wittig chemistry is utterly unnecessary: we report a series of novel ion-pair phosphonium carboxylate reagents which are essentially "storable ylides". These reagents are straightforwardly prepared in excellent yields, and their fluxional nature permits clean olefination of a broad range of aldehydes and even hemiacetals.
- Vetter, Anna C.,Gilheany, Declan G.,Nikitin, Kirill
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supporting information
p. 1457 - 1462
(2021/03/08)
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- Mizoroki-Heck Reaction of Unstrained Aryl Ketones via Ligand-Promoted C-C Bond Olefination
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Mizoroki-Heck reaction of unstrained aryl ketone with acrylate/styrene is accomplished via palladium-catalyzed ligand-promoted C-C bond cleavage. Various (hetero)aryl ketones are compatible in the reaction, affording the alkene product in good to excellent yields. Further applications in the late-stage olefination of some drugs, natural products, and fragrance-derived aryl ketones demonstrate the synthetic utility of this protocol. By employing ketone as both the directing group and the leaving group, 1,2-bifunctionalization is achieved via sequential ortho-C-H alkylation/ipso-Heck olefination.
- Wang, Mei-Ling,Xu, Hui,Li, Han-Yuan,Ma, Biao,Wang, Zhen-Yu,Wang, Xing,Dai, Hui-Xiong
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supporting information
p. 2147 - 2152
(2021/04/05)
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- Nickel-catalyzed Heck reaction of cycloalkenes using aryl sulfonates and pivalates
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Nickel-catalyzed Heck reaction of cycloalkenes delivers unusual conjugated arylated isomers. Nickel(0) catalysts ligated by chelating dialkylphosphines effectively activate not only aryl triflates as electrophiles, but also less reactive aryl mesylates, t
- Zhou, Jianrong Steve,Huang, Xiaolei,Teng, Shenghan,Chi, Yonggui Robin
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supporting information
p. 3933 - 3936
(2021/04/26)
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- Custom-Made Pyrene Photocatalyst-Promoted Desulfonylation of Arylethenyl Sulfones Using Green-Light-Emitting Diodes
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The Sonogashira coupling of 1,3,6,8-tetrabromopyrene with 4-[(-)-β-citronellyloxy]phenylethyne was employed to synthesize 1,3,6,8-tetra[4-(citronellyloxy)phenylethynyl]pyrene. The pyrene derivative catalyzed the reductive desulfonylation of ethenyl sulfones via visible-light irradiation (514 nm green light-emitting diodes) in the presence of i -Pr 2NEt. The β-citronellyloxy groups provided the sufficient solubility to the highly π-expanded pyrene catalyst, and their polar oxygen functionalities enabled the easy separation of the catalyst from the products via column chromatography.
- Watanabe, Hikaru,Nakajima, Kazuki,Ekuni, Kento,Edagawa, Ryota,Akagi, Yuta,Okuda, Yasuhiro,Wakamatsu, Kan,Orita, Akihiro
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p. 2984 - 2994
(2021/03/04)
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- A donor-acceptor complex enables the synthesis of: E -olefins from alcohols, amines and carboxylic acids
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Olefins are prevalent substrates and functionalities. The synthesis of olefins from readily available starting materials such as alcohols, amines and carboxylic acids is of great significance to address the sustainability concerns in organic synthesis. Metallaphotoredox-catalyzed defunctionalizations were reported to achieve such transformations under mild conditions. However, all these valuable strategies require a transition metal catalyst, a ligand or an expensive photocatalyst, with the challenges of controlling the region- and stereoselectivities remaining. Herein, we present a fundamentally distinct strategy enabled by electron donor-acceptor (EDA) complexes, for the selective synthesis of olefins from these simple and easily available starting materials. The conversions took place via photoactivation of the EDA complexes of the activated substrates with alkali salts, followed by hydrogen atom elimination from in situ generated alkyl radicals. This method is operationally simple and straightforward and free of photocatalysts and transition-metals, and shows high regio- and stereoselectivities.
- Chen, Kun-Quan,Shen, Jie,Wang, Zhi-Xiang,Chen, Xiang-Yu
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p. 6684 - 6690
(2021/05/31)
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- Pd-Catalyzed Cross-Coupling of Organostibines with Styrenes to Give Unsymmetric (E)-Stilbenes and (1 E,3 E)-1,4-Diarylbuta-1,3-dienes and Fluorescence Properties of the Products
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A general and effective palladium-catalyzed cross-coupling of organostibines with styrenes to give (E)-olefins was disclosed. By the use of an organostibine reagent, this method can produce unsymmetric (E)-1,2-diarylethylenes and (1E,3E)-1,4-diarylbuta-1,3-dienes in good yields with high E/Z selectivity and good functional group tolerance. Resveratrol and DMU-212 were synthesized in high yield. The protocol can be extended to the synthesis of (1E,3E,5E)-1,6-diphenylhexa-1,3,5-triene in 40% yield. Products 5e, 5f, and 7a showed good photoluminescence quantum yields ranging from 72 to 99%.
- Zhang, Zhao,Zhang, Dejiang,Zhu, Longzhi,Zeng, Dishu,Kambe, Nobuaki,Qiu, Renhua
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supporting information
p. 5317 - 5322
(2021/06/28)
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- Tandem Acceptorless Dehydrogenative Coupling-Decyanation under Nickel Catalysis
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The development of new catalytic processes based on abundantly available starting materials by cheap metals is always a fascinating task and marks an important transition in the chemical industry. Herein, a nickel-catalyzed acceptorless dehydrogenative coupling of alcohols with nitriles followed by decyanation of nitriles to access diversely substituted olefins is reported. This unprecedented C=C bond-forming methodology takes place in a tandem manner with the formation of formamide as a sole byproduct. The significant advantages of this strategy are the low-cost nickel catalyst, good functional group compatibility (ether, thioether, halo, cyano, ester, amino, N/O/S heterocycles; 43 examples), synthetic convenience, and high reaction selectivity and efficiency.
- Babu, Reshma,Balaraman, Ekambaram,Midya, Siba P.,Subaramanian, Murugan,Yadav, Vinita
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p. 7552 - 7562
(2021/06/28)
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- A photocatalyst-free visible-light-mediated solvent-switchable route to stilbenes/vinyl sulfones from β-nitrostyrenes and arylazo sulfones
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Photocatalyst-free visible-light-mediated reactions, based on the presence of a visible-light-absorbing functional group in the starting material itself in order to exclude the often costly, hazardous, degradable and difficult to remove or recover photoredox catalysts, have been gaining momentum recently. We have employed this approach to develop a denitrative photocatalyst-free visible-light-mediated protocol for the arylation/sulfonylation of β-nitrostyrenes employing arylazo sulfones (bench-stable photolabile compounds) in a switchable solvent-controlled manner. Arylazo sulfones served as the aryl and sulfonyl radical precursors under blue LED irradiation for the synthesis oftrans-stilbenes and (E)-vinyl sulfones in CH3CN and dioxane/H2O 2?:?1, respectively. The absence of any metal, photocatalyst and additive; excellent selectivity (E-stereochemistry) and solvent-switchability; and the use of visible light and ambient temperature are the prime assets of the developed method. Moreover, we report the first photocatalyst-free visible light-driven route to synthesize stilbenes and vinyl sulfones from readily available β-nitrostyrenes.
- Chawla, Ruchi,Dutta, P. K.,Jaiswal, Shefali,Yadav, Lal Dhar S.
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supporting information
p. 6487 - 6492
(2021/08/03)
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- A Solid-Phase Assisted Flow Approach to In Situ Wittig-Type Olefination Coupling
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Described herein is the development of a continuous flow, solid-phase triphenylphosphine (PS-PPh3) assisted protocol to facilitate the in situ coupling of reciprocal pairs of halogen and carbonyl functionalised molecular pairs by a Wittig olefination within 15 mins. The protocol entails injecting a single solution (1 : 1 CHCl3 : EtOH) containing the halogenated and carbonyl-based substrates into a continuously flowing stream of CHCl3 : EtOH (1 : 1), passed through a fixed bed of K2CO3 and PS-PPh3. With advancement to the previous PS-PPh3 coupling procedures, the method employs a traditional polystyrene-based immobilisation matrix, the substrate scope of the protocol extended to substituted ketones, secondary alkyl chlorides, and an unprotected maleimide scaffold.
- Aldrich-Wright, Janice R.,Dankers, Christian,Gordon, Christopher P.,Polyzos, Anastasios,Tadros, Joseph
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supporting information
p. 4184 - 4194
(2021/08/24)
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- The two faces of platinum hydrospirophosphorane complexes—Not only relevant catalysts but cytotoxic compounds as well
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Platinum complexes [PtCl2(L)] L = L1, L2 with symmetrical HP (OCH2CMe2NH)2 (L1) and unsymmetrical HP(OCMe2CMe2O)(OCH2CMe2NH) (L2) hydrospirophosphorane (HSP) ligands were demonstrated to play a dual role of catalysts and cytotoxic compounds as well. The structure of new complex [PtCl2(L2)] was confirmed by physicochemical and spectroscopic methods, as well as single X-ray diffraction studies for [PtCl2{P (OCMe2CMe2O)(OCH2CMe2NH2)}]. HSP ligand coordinated to the platinum center in bidentate κ2-P,NH2 chelating mode of fashion. Both complexes were found to exhibit catalytic activity for Heck cross-coupling reactions of iodobenzene with substituted styrenes, with good conversion and yield of stilbenes. Moreover, complexes have been applied as excellent catalysts for highly regioselective hydrosilylation of aromatic and aliphatic terminal olefins, and acetylenes terminal and internal as well. On the other hand, the preliminary biological studies revealed that in the presence of foretinib, drug candidate in clinical trials for the treatment of cancer, platinum complexes revealed increased synergistic effect and efficiently decreased the number of viable cells of triple negative breast cancer MDA-MB-231 cell line.
- Augustyniak, Adam W.,Kowalczyk, Marta,Majchrzak, Mariusz,Nowak, Dorota,Pi?tka, Marta,Siczek, Mi?osz,Simiczyjew, Aleksandra,Skar?yńska, Anna,W?odarczyk, Kinga
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- Synthesis of glucoside-based imidazolium salts for Pd-catalyzed cross-coupling reaction in water
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Sugar-based imidazolium salts (IMSs) represent an outstanding type of material making them eye-catching for a wide variety of applications. Herein, a series of glucoside-based IMSs (Glu-IMSs) combining glucoside and imidazolium head groups with different substituents were synthesized. The catalytic activities of these Glu-IMSs were evaluated by Pd-catalyzed Heck–Mizoroki and Suzuki–Miyaura reactions in water. Among them, the Glu-IMSs contain both –OH and NHCs coordination sites was found to be the most efficient ancillary ligand in comparison with other Glu-IMSs with just single NHCs coordination site. The HR-TEM analysis showed that the palladium nanoparticles stabilized by the Glu-IMSs with an average size of ~4.0 nm was formed in the reaction system, which may be act as an efficient real catalytic species. Under the optimized reaction conditions, a series of novel fluorine-cored organic small molecule functional materials were synthesized with favorable yields.
- Du, Ziyi,Lu, Dongliang,Pan, Yan,Xie, Qian,Xue, Jun,Yuan, Yangyang,Zhou, Xin,Zhou, Zhonggao
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supporting information
(2020/08/06)
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- Catalytic and antibacterial properties of 3-dentate carboxamide Pd/Pt complexes obtained via a benign route
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The complexes PdII(qcq)(OAc) and PtII(qcq)Cl have been synthesized using environmentally benign synthesized ligands and characterized by elemental analyses: Fourier transform infrared spectroscopy, UV–visible spectroscopy, 1H NMR spectroscopy, and X-ray diffraction. The catalytic activity of the complex was assessed, in different media, for the Mizoroki–Heck coupling reaction for typical aryl halides and terminal olefins under aerobic conditions. Since the base and the solvent were found to influence the efficiency of the reaction, reaction conditions, temperature, time, and the amount of K3PO4 and a mixture of H2O/PEG, were optimized. We found, for the Mizoroki–Heck reaction coupling less reactive aryl chloride derivatives with olefins, promising activity for palladium catalysts. The electrochemical behavior of Hqcq and the Pd(II) complex was investigated by cyclic voltammetry and irreversible PdII/I reductions were observed. Hqcq and the Pd(II) and Pt(II) complexes were also screened for their in vitro antibacterial activity. They showed promising antibacterial activity comparable to that of the antibiotic penicillin.
- Kiani, Mahsa,Bagherzadeh, Mojtaba,Meghdadi, Soraya,Fadaei-Tirani, Farzaneh,Schenk-Jo?, Kurt,Rabiee, Navid
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- Palladium schiff base complex immobilized on magnetic nanoparticles: An efficient and recyclable catalyst for Mizoroki and Matsuda-Heck coupling
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The present work elucidates the catalytic efficiency of palladium Schiff base complex immobilized on amine functionalized magnetic nanoparticles for Heck coupling of structurally different aryl halide/arenediazonium tetrafluoroborate with styrene/acrylate/acrylonitrile. Matsuda-Heck coupling proceeds in aqueous media at room temperature whereas Mizoroki-Heck coupling was carried out at 80 °C. Both reactions were successfully furnished with low catalyst loading. The catalyst was easily separated from reaction mixture and reused up to six times without significant loss of catalytic activity.
- Vibhute, Sandip P.,Mhaldar, Pradeep M.,Shejwal, Rajendra V.,Rashinkar, Gajanan S.,Pore, Dattaprasad M.
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supporting information
(2020/03/23)
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- Exploring Homogeneous Conditions for Mild Buchwald-Hartwig Amination in Batch and Flow
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Cross-couplings are among the most frequently used reactions in complex molecule synthesis. However, the requirement of stoichiometric base can cause challenges. Harsh, insoluble inorganic bases can lead to poor tolerance of sensitive functional groups, scale-up issues, and difficult adaptation to continuous flow platforms. Herein, we describe the use of high throughput experimentation to identify a number of conditions that enable Buchwald-Hartwig reactions to be carried out using readily available ligands (e.g., XantPhos) with DBU as a soluble, functional-group-tolerant, homogeneous base. Application of this system to diverse aminations in batch and flow are demonstrated, as is the translation of this technique to performing continuous Mizoroki-Heck and Sonogashira coupling reactions.
- Kashani, Saeed K.,Jessiman, Jacob E.,Newman, Stephen G.
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supporting information
p. 1948 - 1954
(2020/03/13)
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