- SULFAMATE DERIVATIVE COMPOUNDS FOR USE IN TREATING OR ALLEVIATING A PSYCHIATRIC DISORDER
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The present invention relates to a pharmaceutical composition for treating and/or alleviating a psychiatric disorder comprising a sulfamate derivative compound and/or a pharmaceutically acceptable salt thereof as an active ingredient. Furthermore, the present invention relates to a pharmaceutical composition for inducing anti-stress, anti-anxiety and/or anti-depressant activities comprising a sulfamate derivative compound and/or a pharmaceutically acceptable salt thereof as an active ingredient.
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Paragraph 526-529; 643-647
(2022/04/03)
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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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- Oxoammonium-Mediated Allylsilane–Ether Coupling Reaction
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A new C(sp3)?H functionalization reaction consisting of the oxidative α-allylation of allyl- and benzyl- methyl ethers has been developed. The C?C coupling could be carried out under mild conditions thanks to the use of cheap and green oxoammonium salts. The scope of the reaction was studied over 27 examples, considering the nature of the substituents on the two coupling partners.
- Carlet, Federica,Bertarini, Greta,Broggini, Gianluigi,Pradal, Alexandre,Poli, Giovanni
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supporting information
p. 2162 - 2168
(2021/04/02)
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- N-Heterocyclic Carbene/Carboxylic Acid Co-Catalysis Enables Oxidative Esterification of Demanding Aldehydes/Enals, at Low Catalyst Loading
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We report the discovery that simple carboxylic acids, such as benzoic acid, boost the activity of N-heterocyclic carbene (NHC) catalysts in the oxidative esterification of aldehydes. A simple and efficient protocol for the transformation of a wide range of sterically hindered α- and β-substituted aliphatic aldehydes/enals, catalyzed by a novel and readily accessible N-Mes-/N-2,4,6-trichlorophenyl 1,2,4-triazolium salt, and benzoic acid as co-catalyst, was developed. A whole series of α/β-substituted aliphatic aldehydes/enals hitherto not amenable to NHC-catalyzed esterification could be reacted at typical catalyst loadings of 0.02–1.0 mol %. For benzaldehyde, even 0.005 mol % of NHC catalyst proved sufficient: the lowest value ever achieved in NHC catalysis. Preliminary studies point to carboxylic acid-induced acceleration of acyl transfer from azolium enolate intermediates as the mechanistic basis of the observed effect.
- Berkessel, Albrecht,Biswas, Animesh,Harnying, Wacharee,Sudkaow, Panyapon
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supporting information
p. 19631 - 19636
(2021/08/09)
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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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- C–C Cross-Coupling Reactions of Organosilanes with Terminal Alkenes and Allylic Acetates Using PdII Catalyst Supported on Starch Coated Magnetic Nanoparticles
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Starch coated magnetic nanoparticles supported palladium catalyst has been explored to perform C–C cross coupling reactions, such as oxidative Heck coupling and Tsuji–Trost allylic coupling using organosilicon compounds as one of the coupling partners. The biopolymer coated magnetic catalyst was very easy to recover magnetically and was efficiently recycled in the subsequent batches. All the reactions were performed in air and thus the necessity of air and moisture free reaction condition is avoided. The present protocols show wide substrate scope and good yields of the products.
- Patra, Debabrata,Panja, Subir,Saha, Amit
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p. 878 - 883
(2020/02/13)
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- Amidoxime modified PAN supported palladium complex: A greener and efficient heterogeneous catalyst for heck reaction
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Development of a facile and greener approach for Heck reaction using a modified PAN supported palladium catalyst is described. The preparation of the catalyst involves a simple process through amidoxime modification of nitrile group in Polyacrylonitrile (PAN), followed by the complexation with Palladium chloride (PdCl2). The resulting supported catalyst was characterized by spectroscopic analyses and further by computational studies. This polymer supported Palladium complex displayed excellent catalytic activity in Heck coupling reaction of a series of activated alkenes and aryl halides and afforded the corresponding coupling products upto 96% isolated yield. After the reaction, the catalyst was easily recovered by simple filtration and recycled with excellent stability and activity even after 5 runs. This is the first report on the use of amidoxime functionalized PAN- Palladium (II) complex as a heterogeneous catalyst in Heck coupling reaction.
- Sruthi, Pambingal Rajan,Sarika, Vijayalekshmi,Suku, Arya,Krishnan, Aravind,Anas, Saithalavi
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- Pd/Cu-free Heck and Sonogashira coupling reactions applying cobalt nanoparticles supported on multifunctional porous organic hybrid
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A new heterogeneous cobalt catalyst has been synthesized by immobilizing Co species onto a nitrogen-rich porous organic polymer (Co@imine-POP). The heterogeneous catalyst synthesized was efficient in Heck and Sonogashira cross-coupling reactions in green media under mild reaction conditions without inert air and phase transfer agents. This phosphine-, copper-, and palladium-free catalyst was stable under the reaction conditions and could be reused for at least eight successive runs without a discernible decrease in its catalytic activity.
- Hajipour, Abdol R.,Khorsandi, Zahra
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- A Bipyridine-Palladium Derivative as General Pre-Catalyst for Cross-Coupling Reactions in Deep Eutectic Solvents
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A versatile and DES-compatible bipyridine palladium complex has been developed as a general pre-catalyst for different cross-coupling reactions (Hiyama, Suzuki-Miyaura, Heck-Mizoroki and Sonogashira) in deep eutectic solvents. Hydrogen bond capacity of the ligand allows to keep the excellent level of results previously obtained in classical organic solvents. Palladium pre-catalyst showed a high catalytic activity for many cross-coupling reactions, demonstrating a great versatility and applicability. Also, this methodology employs sustainable solvents as a reaction medium and highlights the potential of DES as alternative solvents in organometallic catalysis. The catalyst and DES were easily and successfully recycled. The formation of PdNPs in DES has been confirmed by TEM and XPS analysis and their role as catalyst by mercury test. The dynamic coordination of bipyridine-type ligand in the palladium complex formation has been studied via UV/Vis. (Figure presented.).
- Saavedra, Beatriz,González-Gallardo, Nerea,Meli, Alessandro,Ramón, Diego J.
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supporting information
p. 3868 - 3879
(2019/07/12)
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- Biochar as heterogeneous support for immobilization of Pd as efficient and reusable biocatalyst in C–C coupling reactions
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Biochar is a stable and carbon-rich solid which has a high density of carbonyl, hydroxyl and carboxylic acid functional groups on its surface. In this work, the surface of biochar nanoparticles (BNPs) was modified with 3-choloropropyltrimtoxysilane and further 2-(thiophen-2-yl)-1H-benzo[d]imidazole was anchored on its surface. Then, palladium nanoparticles were fabricated on the surface of the modified BNPs and further the catalytic application was studied as recyclable biocatalyst in carbon–carbon coupling reactions such as Suzuki–Miyaura and Heck–Mizoroki cross-coupling reactions. The structure of the catalyst was characterized using scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, thermogravimetric analysis, X-ray diffraction and atomic absorption spectroscopy. The catalyst can be reused several times without a decrease in its catalytic efficiency. In addition to the several advantages reported, application of biochar as catalyst support for the first time is a major novelty of the present work.
- Moradi, Parisa,Hajjami, Maryam,Valizadeh-Kakhki, Fatemeh
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- Magnetic MCM-41 nanoparticles as a support for the immobilization of a palladium organometallic catalyst and its application in C-C coupling reactions
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In this study, the surface of magnetic MCM-41 nanoparticles (MCM-41/Fe3O4) was modified by 3-Aminopropyltriethoxysilane (APTES) and further, 1-methyl imidazole was anchored on their surface using cyanuric chloride as a linker. Then, Pd2+ ions were immobilized on the surface of the modified MCM-41/Fe3O4 (Pd-imi-CC@MCM-41/Fe3O4), and its application was studied as a magnetically recyclable nanocatalyst in carbon-carbon coupling reactions between a wide range of aryl halides and butyl acrylate, methyl acrylate, acrylonitrile, phenylboronic acid, or 3,4-difluorophenylboronic acid under the conditions of a phosphine-free ligand and an air atmosphere. This catalyst has the advantages of both the Fe3O4 nanoparticles and mesoporous MCM-41. The structure of the catalyst was characterized via TEM, SEM, EDS, WDX, N2 adsorption-desorption isotherm, XRD, TGA, FT-IR, and AAS. Also, the recovered catalyst was characterized via SEM, AAS and FT-IR. All the products from the carbon-carbon coupling reaction were obtained with excellent yields and high TON and TOF values, which indicate the high efficiency and activity of this catalyst. The selectivity of this catalyst was studied with various aryl halides bearing different functional groups. Furthermore, the heterogeneity and stability of Pd-imi-CC@MCM-41/Fe3O4 was studied via AAS, and leaching and poisoning tests. According to the results, this heterogeneous catalyst can be reused several times.
- Tahmasbi, Bahman,Ghorbani-Choghamarani, Arash
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supporting information
p. 14485 - 14501
(2019/09/30)
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- Novel multi-dentate phosphines for Pd-catalyzed alkoxycarbonylation of alkynes promoted by H2O additive
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A series of novel multi (bi-/tri-/tetra-)-dentate phosphines with good robustness against water and oxygen were synthesized and fully characterized. It was found that the developed ionic tri-dentate phosphine (L2′) enabled Pd-catalyzed alkoxycarbonylation of alkynes most efficiently while H2O was used as an additive instead of acid. As for L2′, its unique steric configuration with two types of potential P-P chelation modes (P?P distance of 4.31 ? and 4.36 ? respectively) to Pd-centre rendered the corresponding Pd-catalyst high activity and good stability for alkoxycarbonylation of alkynes. The in situ FT-IR analysis also verified that the formation and stability of Pd–H active species were greatly facilitated with the presence of L2′ as well as H2O additive. In addition, as an ionic phosphine, L2′ based PdCl2(MeCN)2 system immobilized in RTIL of [Bmim]NTf2 could be recycled for 7 runs without obvious activity loss or metal leaching.
- Yang, Da,Liu, Lei,Wang, Dong-Liang,Lu, Yong,Zhao, Xiao-Li,Liu, Ye
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p. 236 - 244
(2019/02/19)
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- Synthesis of Tetrahydroisoquinolines by Visible-Light-Mediated 6- exo -trig Cyclization of α-Aminoalkyl Radicals
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Starting from the respective tertiary α-silylmethyl amines, the intramolecular cyclization of α-aminoalkyl radicals to Michael acceptors produced tetrahydroisoquinolines. The reaction conditions included the use of 5 molpercent of an iridium photoredox catalyst, dimethylformamide as the solvent, and equimolar amounts of water and cesium carbonate as the additives. 13 substrates were synthesized from ortho -alkylbenzaldehydes in a three-step procedure involving a carbonyl condensation, a radical bromination, and a substitution by a secondary α-silylmethyl amine. After optimization of the photocyclization, the reaction delivered tetrahydroisoquinolines in moderate to high yields (41-83percent). A facial diastereoselectivity (dr ? 80:20) was observed with chiral substrates and a crystal structure provided evidence for the relative configuration of the major diastereoisomer. A catalytic cycle with direct electron transfer to the photoexcited metal catalyst is proposed.
- Bach, Thorsten,Grübel, Michael,Jandl, Christian
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supporting information
p. 1825 - 1829
(2019/09/09)
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- Discovery of novel piperonyl derivatives as diapophytoene desaturase inhibitors for the treatment of methicillin-, vancomycin- and linezolid-resistant Staphylococcus aureus infections
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Inhibition of S. aureus diapophytoene desaturase (CrtN) could serve as an alternative approach for addressing the tricky antibiotic resistance by blocking the biosynthesis of carotenoid pigment which shields the bacterium from host oxidant killing. In this study, we designed and synthesized 44 derivatives with piperonyl scaffold targeting CrtN and the structure-activity relationships (SARs) were examined extensively to bring out the discovery of 21b with potent efficacy and better hERG safety profile compared to the first class CrtN inhibitor benzocycloalkane derivative 2. Except the excellent pigment inhibitory activity against wild-type S. aureus, 21b also showed excellent pigment inhibition against four pigmented MRSA strains. In addition, H2O2 killing and human whole blood killing assays proved 21b could sensitize S. aureus to be killed under oxidative stress conditions. Notably, the murine study in vivo validated the efficacy of 21b against pigmented S. aureus Newman, vancomycin-intermediate S. aureus Mu50 and linezolid-resistant S. aureus NRS271.
- Wei, Hanwen,Mao, Fei,Ni, Shuaishuai,Chen, Feifei,Li, Baoli,Qiu, Xiaoxia,Hu, Linghao,Wang, Manjiong,Zheng, Xinyu,Zhu, Jin,Lan, Lefu,Li, Jian
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p. 235 - 251
(2018/01/17)
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- Syntheses, characterization, solution behavior and catalytic activity of trans-[(guanidine)2PdX2] (X?=?Cl and OC(O)R; R?=?Me, Ph and tBu) in Heck–Mizoroki coupling reactions involving chloroarenes/methyl acrylate
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Trans-[{(ArNH)2C[dbnd]NAr}2PdX2] (Ar = 2,5-Me2C6H3; X = Cl (1) and OC(O)R; R = Me (2), Ph (3), and tBu (4)) were isolated in high yields and characterized by elemental analysis, IR, and NMR (1H and 13C) spectroscopy. The molecular structures of the aforementioned complexes were determined by single crystal X-ray diffraction which revealed trans syn anti-anti (1·CHCl3), trans anti anti-syn (2·CHCl3 and 3·C7H8) and trans anti anti-anti (4) stereochemistry in solid state. Complexes 2·CHCl3, 3·C7H8 and 4 contain a pair of R11(8) rings stabilized by an intramolecular N–H?O hydrogen bond between the guanidine ligand and the carboxylate moiety. The influence of shape and size of the anion upon the stereochemistry of the complexes in the solid state and in solution are discussed. VT 1H NMR spectroscopic studies carried out on samples of 1 and 3 revealed the presence of a mixture of two rotamers in solution which arise due to the restricted [dbnd]C–N(H)Ar single bond rotation of the guanidine ligand in both complexes. Complexes 1–4 were shown to be active catalysts even when used in 0.001 mol% in Heck–Mizoroki coupling reactions involving chlorobenzene and methyl acrylate. The scope of 1 in Heck–Mizoroki coupling reactions involving methyl acrylate and nine distinct chloroarenes were explored at 0.01 mol% which afforded the coupling products in 81?96% yields.
- Elumalai, Palani,Ujjval, Rishabh,Nethaji, Munirathinam,Thirupathi, Natesan
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p. 313 - 322
(2018/06/20)
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- Kryptofix 5 as an inexpensive and efficient ligand for the palladium-catalyzed Mizoroki-Heck reaction
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A novel complex of PdCl2 with a multidentate cryptand ligand, Kryptofix 5, has been prepared and characterized by various techniques including 1H- and 13C NMR spectroscopy, Fourier transform infrared (FT-IR), Raman, ultraviolet and visible (UV-VIS) spectroscopy, inductively coupled plasma (ICP), CHN elemental and energy dispersive X-ray analysis (EDX). This heat- and air-stable complex was utilized as a highly active catalyst for the Mizoroki-Heck reaction of aryl halides with various olefins. Interestingly, it was found that aryl bromides as well as aryl iodides were efficiently cross-coupled with terminal alkenes at 130?°C in 10?min. Furthermore, the least reactive aryl chlorides reacted with styrene to obtain the desired products in acceptable yields.
- Movassagh, Barahman,Ranjbari, Shabnam
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- Synthesis of Highly Substituted Arenes via Cyclohexadiene-Alkene C-H Cross Coupling and Aromatization
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The development of a cross-coupling method for the regioselective β-alkenylation of 2,5-cyclohexadiene carboxylic acid derivatives to form ortho-alkenylarenes through in situ decarboxylation and aromatization is described. The carboxylic acid functionality is used as a traceless directing group for efficient and mild β-alkenylation. The modular sequence comprises a reductive Birch α-alkylation, ionic ?-alkylation followed by a Pd-catalyzed decarboxylative β-alkenylation with subsequent aromatization resulting in an overall three-fold ipso-para-ortho functionalization of readily accessed benzoic acid derivatives. Efficient synthesis of various alkyl-alkenylarenes under mild conditions in moderate to excellent yields is presented.
- Bhunia, Anup,Studer, Armido
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p. 1213 - 1217
(2018/02/14)
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- Pd nanoparticles immobilized on magnetic chitosan as a novel reusable catalyst for green Heck and Suzuki cross-coupling reaction: In water at room temperature
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A novel type of magnetically responsive chitosan nanocomposite was successfully synthesized as a green and high powerful palladium-based heterogeneous catalyst and its efficiency in Heck and Suzuki cross-coupling was evaluated. This catalyst promote a large library of functional substrates of these reactions under mild and sustainable conditions (water or ethanol as solvent, at room temperature, in significantly short reaction time (20?minutes)) and stand as recyclable, metal scavenging catalytic systems.
- Hajipour, Abdol R.,Sadeghi, Ali R.,Khorsandi, Zahra
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- Probing the Evolution of Palladium Species in Pd@MOF Catalysts during the Heck Coupling Reaction: An Operando X-ray Absorption Spectroscopy Study
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The mechanism of the Heck C-C coupling reaction catalyzed by Pd@MOFs has been investigated using operando X-ray absorption spectroscopy (XAS) and powder X-ray diffraction (PXRD) combined with transmission electron microscopy (TEM) analysis and nuclear magnetic resonance (1H NMR) kinetic studies. A custom-made reaction cell was used, allowing operando PXRD and XAS data collection using high-energy synchrotron radiation. By analyzing the XAS data in combination with ex situ studies, the evolution of the palladium species is followed from the as-synthesized to its deactivated form. An adaptive reaction mechanism is proposed. Mononuclear Pd(II) complexes are found to be the dominant active species at the beginning of the reaction, which then gradually transform into Pd nanoclusters with 13-20 Pd atoms on average in later catalytic turnovers. Consumption of available reagent and substrate leads to coordination of Cl- ions to their surfaces, which causes the poisoning of the active sites. By understanding the deactivation process, it was possible to tune the reaction conditions and prolong the lifetime of the catalyst.
- Yuan, Ning,Pascanu, Vlad,Huang, Zhehao,Valiente, Alejandro,Heidenreich, Niclas,Leubner, Sebastian,Inge, A. Ken,Gaar, Jakob,Stock, Norbert,Persson, Ingmar,Martín-Matute, Belén,Zou, Xiaodong
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supporting information
p. 8206 - 8217
(2018/06/22)
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- Rapid Access to Ortho-Alkylated Vinylarenes from Aromatic Acids by Dearomatization and Tandem Decarboxylative C-H Olefination/Rearomatization
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A two-step straightforward method for the preparation of ortho-alkylated vinylarenes from readily available benzoic acids is described. The synthetic route involves the dearomatization of benzoic acids by Birch reduction providing alkylated cyclohexa-2,5-dienyl-1-carboxylic acids. The diene subsequently undergoes a decarboxylative C-H olefination followed by rearomatization to deliver ortho-alkylated vinylarene. Mechanistic studies suggest that a Pd/Ag bimetallic catalytic system is important in the tandem decarboxylative C-H olefination/rearomatization step.
- Tsai, Hung-Chang,Huang, Yen-Hsiang,Chou, Chih-Ming
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supporting information
p. 1328 - 1332
(2018/03/09)
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- The Catalytic Asymmetric Mukaiyama–Michael Reaction of Silyl Ketene Acetals with α,β-Unsaturated Methyl Esters
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α,β-Unsaturated esters are readily available but challenging substrates to activate in asymmetric catalysis. We now describe an efficient, general, and highly enantioselective Mukaiyama–Michael reaction of silyl ketene acetals with α,β-unsaturated methyl esters that is catalyzed by a silylium imidodiphosphorimidate (IDPi) Lewis acid.
- Gatzenmeier, Tim,Kaib, Philip S. J.,Lingnau, Julia B.,Goddard, Richard,List, Benjamin
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supporting information
p. 2464 - 2468
(2018/02/06)
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- Enantioselective Intermolecular Addition of Aliphatic Amines to Acyclic Dienes with a Pd-PHOX Catalyst
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We report a method for the catalytic, enantioselective intermolecular addition of aliphatic amines to acyclic 1,3-dienes. In most cases, reactions proceed efficiently at or below room temperature in the presence of 5 mol % of a Pd catalyst bearing a PHOX ligand, generating allylic amines in up to 97:3 er. The presence of an electron-deficient phosphine within the ligand not only leads to a more active catalyst but also is critical for achieving high site selectivity in the transformation.
- Adamson, Nathan J.,Hull, Ethan,Malcolmson, Steven J.
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supporting information
p. 7180 - 7183
(2017/06/05)
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- Oxidative coupling of Michael acceptors with aryl nucleophiles produced through rhodium-catalyzed C-C bond activation
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Utilizing rhodium catalysis, aryl nucleophiles generated via carbon-carbon single bond activation successfully undergo oxidative coupling with Michael acceptors. The reaction scope encompasses a broad range of nucleophiles generated from quinolinyl ketones as well as a series of electron deficient terminal alkenes, illustrating the broad potential of intersecting carbon-carbon bond activation with synthetically useful coupling methodologies. The demonstrated oxidative coupling produces a range of cinnamyl derivatives, several of which are challenging to prepare via conventional routes.
- Gregerson, Caroline E.,Trentadue, Kathryn N.,Phipps, Erik J. T.,Kirsch, Janelle K.,Reed, Katherine M.,Dyke, Gabriella D.,Jansen, Jacob H.,Otteman, Christian B.,Stachowski, Jessica L.,Johnson, Jeffrey B.
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p. 5944 - 5948
(2017/07/25)
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- Arylhydrazones Derivatives Containing a Benzothiazole Moiety, Efficient Ligands in the Palladium-Catalyzed Mizoroki–Heck and Suzuki–Miyaura Cross-coupling Reactions under IR Irradiation
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A simple arylhydrazone containing the benzothiazole moiety which may be used as an efficient ligand in the palladium-catalyzed Mizoroki–Heck and Suzuki–Miyaura cross-coupling reactions, under infrared irradiation as an alternative source of energy, is presented. The reactions proceeded with extremely high efficiency under mild conditions and produced very good yields.
- Ortega-Jiménez, Fernando,Penieres-Carrillo, José Guillermo,López-Cortés, José Guadalupe,Carmen Ortega-Alfaro,Lagunas-Rivera, Selene
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p. 1881 - 1888
(2017/09/12)
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- Pd/Cu-free Heck and Sonogashira cross-coupling reaction by Co nanoparticles immobilized on magnetic chitosan as reusable catalyst
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Chitosan (CS) is a porous, self-standing, nanofibrillar microsphere that can be used as a metal carrier. Amino groups on CS enable to modulate cobalt coordination using a safe organic ligand (methyl salicylate). This catalyst efficiently promotes Heck cross-coupling of a large library of functional substrates under mild and sustainable conditions (polyethylene glycol as solvent at 80 °C in a short time (1 h)). The cobalt complex was also used as a heterogeneous, efficient, inexpensive, and green catalyst for Sonogashira cross-coupling reactions. The reactions of various aryl halides and phenylacetylene provided the corresponding products in moderate to good yields. More importantly, this phosphine, copper, and palladium-free catalyst was stable under the reaction conditions and could be easily reused using an external magnet for at least five successive runs without a discernible decrease in its catalytic activity.
- Hajipour, Abdol R.,Rezaei, Fatemeh,Khorsandi, Zahra
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supporting information
p. 1353 - 1361
(2017/08/18)
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- Deep Eutectic Solvent Compatible Metallic Catalysts: Cationic Pyridiniophosphine Ligands in Palladium Catalyzed Cross-Coupling Reactions
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Cationic pyridiniophosphine ligands have been synthetized in an attempt to develop a deep eutectic solvents (DESs) compatible catalytic systems. These ligands, in combination with PdCl2, have been successfully applied to different palladium-catalyzed cross coupling reactions, such as Suzuki–Miyaura, Sonogashira, or Heck couplings. While traditional palladium ligands in DES medium failed to reproduce the results obtained in VOC solvents, these cationic phosphines improved the catalytic activity of palladium as no other traditional ligand could in such a polar medium. In addition, the recyclability of these processes was studied, allowing us to reuse both, catalyst and solvent up to 5 times in Suzuki and Sonogashira reactions without a significant drop in the catalytic activity. Regarding the structure of the Pd catalysts, titration, NMR, and DFT studies have clearly demonstrated the coordination properties of the DES-compatible cationic phosphine ligands.
- Marset, Xavier,Khoshnood, Abbas,Sotorríos, Lia,Gómez-Bengoa, Enrique,Alonso, Diego A.,Ramón, Diego J.
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p. 1269 - 1275
(2017/04/14)
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- In-situ-generated palladium nanoparticles in novel ionic liquid: an efficient catalytic system for Heck–Matsuda coupling
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Abstract: A green, convenient, ecological and recyclable method comprising dual functionalized, task-specific, ionic liquid (IL)-triggered, in situ-generated Pd nanoparticles (NPs) and their catalytic application for Heck–Matsuda coupling of olefins is described. Both arenediazonium tetrafluoroborate and silica sulphate salts are coupled with olefins under ligand-free and aerobic conditions at ambient temperature furnishing excellent yields of products. The Ionic liquid used acts as a reducing as well as stabilizing agent for in situ-generated Pd NPs. The formed NPs were characterized by transmission electron microscopy (TEM) analysis, having a size below 50?nm, and exhibited high catalytic activity. The catalytic system can be reused for eight times effectively without any significant loss of activity. The method was found to be highly stereo-specific, giving exclusively the ‘E’ isomer.
- Gaikwad,Undale,Patil,Pore,Korade,Kamble
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p. 4445 - 4458
(2017/07/22)
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- Functionalized β-cyclodextrin as supramolecular ligand and their Pd(OAc)2 complex: Highly efficient and reusable catalyst for Mizoroki-Heck cross-coupling reactions in aqueous medium
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A novel class of water soluble palladium complexes with recognition abilities based on functionalized β-cyclodextrin has been synthesized. The complex demonstrated high catalytic activity and a supramolecular platform for phosphine-free Mizoroki-Heck cross-coupling reactions in water. The efficient arylation of alkenes was carried out using different iodo- and bromo-arenes with good to excellent yields (up to 96%). The advantages, like recyclability of catalysts, operational simplicity and accessibility in aqueous medium, make this protocol eco-friendly.
- Dindulkar, Someshwar D.,Jeong, Daham,Kim, Hwanhee,Jung, Seunho
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- Infrared irradiation or microwave assisted cross-coupling reactions using sulfur-containing ferrocenyl-palladacycles
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The synthesis of four new sulfur-containing palladacycles 3a-d [FcC(S)OEtPdClZR3, where: 3a, ZR3: PPh3; 3b, ZR3: P(o-Tol)3; 3c, ZR3: PMe3; 3d, ZR3: SbPh3] from ferrocenyl thionoester 1 [FcC(S)OEt] in good yields is reported. The catalytic applications of these cyclopalladated complexes in Heck and Suzuki cross-coupling reactions were also evaluated, in combination with infrared or microwave as energy sources. The coupled products of these reactions were obtained in good to excellent yields, short reaction times and low catalyst loading.
- Balam-Villarreal,Sandoval-Chávez,Ortega-Jiménez,Toscano,Carreón-Castro,López-Cortés,Ortega-Alfaro
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- Catalytic asymmetric bromochlorination of aromatic allylic alcohols promoted by multifunctional Schiff base ligands
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It was found that the tridentate O,N,O-type Schiff base ligand bearing suitable substituents was a highly effective promoter in the catalytic asymmetric bromochlorination reaction, in which the corresponding aromatic bromochloroalcohols with vicinal halogen-bearing stereocenters were formed with perfect regioselectivity, with moderate to excellent enantioselectivities (up to 93% ee), and with good yields and chemoselectivities.
- Huang, Wei-Sheng,Chen, Li,Zheng, Zhan-Jiang,Yang, Ke-Fang,Xu, Zheng,Cui, Yu-Ming,Xu, Li-Wen
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supporting information
p. 7927 - 7932
(2016/08/30)
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- Regioselective Heck reaction catalyzed by Pd nanoparticles immobilized on DNA-modified MWCNTs
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This is the first report of regioselective Heck reaction of aryl iodides with 2,3-dihydrofuran using heterogonous nanocatalyst. Herein, palladium nanoparticles is immobilized on DNA-modified multi walled carbon nanotubes and characterized by FT-IR spectroscopy, UV-vis spectroscopy, field emission scanning electron microscopy, X-ray diffraction, transmission electron microscopy, inductively coupled plasma and elemental analysis. DNA as a well-defined structure and biodegradable natural polymer generate the palladium catalyst which showed high activity in common and regioselective Heck reaction in excellent yields and good selectivity under ligand-free and mild reaction conditions. Moreover, the catalyst could be recovered and reused at least nine times without any considerable loss of its catalytic activity.
- Hajipour, Abdol R.,Khorsandi, Zahra,Farrokhpour, Hossein
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p. 59124 - 59130
(2016/07/06)
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- Compositions containing ionic liquids and their uses, in particular in organic synthesis
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An ionic liquid is used as liquid matrix for organic synthesis in homogeneous phase on soluble support, the ionic liquid being presented in liquid or solid form at ambient temperature, of formula A1+X1?, A1+ representing a cation, functional or non-functional, or a mixture of cations in which either none of the cations is functional or at least one of the cations is functional, and X1? an anion, functional or non-functional, or a mixture of anions in which either none of the anions is functional or at least one of the anions is functional.
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Page/Page column 45; 46; 47
(2016/10/17)
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- SULFAMATE DERIVATIVE COMPOUND FOR USE IN PREVENTING OR TREATING EPILEPSY
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The present invention relates to a pharmaceutical composition for treating or preventing epilepsy containing a sulfamate derivative compound and/or pharmaceutically acceptable salt thereof as an active ingredient. Furthermore, the present invention relates to a method for treatment or prevention epilepsy comprising administering a sulfamate derivative compound in a pharmaceutically effective amount to a subject in need of treatment or prevention of epilepsy.
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Page/Page column 38
(2015/06/25)
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- Trimetallic PEPPSI-Type Palladium N-Heterocyclic Carbene Complexes - Improved Catalyst Lifetime in the Mizoroki-Heck Coupling Reaction
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A series of mono- and dendritic trimetallic PEPPSI-type (pyridine-enhanced precatalyst preparation stabilization and initiation) complexes bearing N-heterocyclic carbene (NHC) ligands containing a protected amine in the form of an ethylphthalimido group h
- Martnez-Olid, Francisco,Andrs, Romn,Flores, Juan C.,Gmez-Sal, Pilar
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p. 4076 - 4087
(2015/09/01)
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- NCN pincer palladium complexes based on 1,3-dipicolyl-3,4,5,6-tetrahydropyrimidin-2-ylidenes: Synthesis, characterization and catalytic activities
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The synthesis of novel pincer palladium complexes containing ring expanded six-membered N-heterocyclic carbenes (NHCs) via direct metallation of the precursors tetrahydropyrimidin-1-ium hexafluorophosphates in the presence of NaN(SiMe3)2 is presented. The structure has been characterized unambiguously by X-ray single crystal analysis. Catalytic activity investigation showed that the complexes catalyzed the Heck reaction of aryl bromides with acrylate/styrene efficiently when using Et3N as base and DMA as solvent.
- Yang, Liangru,Zhang, Xinchi,Mao, Pu,Xiao, Yongmei,Bian, Huanyu,Yuan, Jinwei,Mai, Wenpeng,Qu, Lingbo
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p. 25723 - 25729
(2015/10/20)
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- Immobilized palladium nanoparticles on potassium zirconium phosphate as an efficient recoverable heterogeneous catalyst for a clean Heck reaction in flow
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Palladium nanoparticles on layered potassium α-zirconium phosphate (PdNP/α-ZrPK) with high palladium loading (10.6 wt%) have been prepared and used as catalyst in low amount (0.1 mol% of Pd) in the Heck reaction of methyl acrylate and styrene with a series of aryl iodides in CH3CN/H2O azeotrope as a green medium. The procedure has been optimized under flow conditions obtaining an extremely low waste production (E-factor) and allowing to isolate the final product with very low residual palladium content without any purification step.
- Petrucci, Chiara,Cappelletti, Matteo,Piermatti, Oriana,Nocchetti, Morena,Pica, Monica,Pizzo, Ferdinando,Vaccaro, Luigi
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- Ligand-free C-C and C-N cross-couplings with Pd/Nf-G nanocomposite
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Abstract The catalytic activity of electrochemical deposited Pd nanoparticles on nafion-graphene support was examined for Buchwald-Hartwig amination reaction and Heck coupling reaction. The developed protocol is very efficient and ecofriendly, providing excellent product yield. The Pd/Nf-G catalyst can be used up to four cycles with slight decrease in catalytic activity.
- Shelkar, Radheshyam S.,Shendage, Suresh S.,Nagarkar, Jayashree M.
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supporting information
p. 4463 - 4467
(2015/06/30)
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- Palladium-Catalyzed Arylation of Olefins by Triarylphosphines via C-P Bond Cleavage
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C-H Arylation of olefins by triarylphosphines via C-P bond cleavage has been achieved with either Pd0 or PdII catalysts. A variety of olefins and triarylphosphines are tolerated, and we inferred that both Pd0 and PdII could function directly without pre-oxidation or pre-reduction.
- Lu, Dapeng,Xu, Yu,Liu, Wenjing,Guo, Lijuan,Sun, Xingxia
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p. 116 - 122
(2015/10/19)
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- Scope and Limitation of the Microwave-Assisted Catalytic Wittig Reaction
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We have developed a microwave-assisted catalytic Wittig reaction. In this paper, we give full account of the scope and limitations of this reaction. A screening of various commercially available phosphine oxides as precatalysts revealed Bu3P=O to be the most promising candidate. We tested 10 silanes for the in situ reduction of the phosphine oxide to generate Bu3P as the actual catalyst. Different epoxides were tested as masked bases. In this context, cyclohexene oxide as well as butylene oxide proved to be suitable. The reaction could be carried out at 125 C, but higher yields and E/Z selectivities were obtained at 150 °C. Under the optimised reaction conditions, more than 40 examples for the conversion of various aldehydes into the corresponding alkenes are reported. The products were obtained in yields of up to 88 with high E selectivities. Moreover, we also describe the further screening of several chiral phosphines as catalysts for the microwave-assisted enantioselective catalytic Wittig reaction. The scope and limitations of the microwave-assisted catalytic Wittig reaction have been evaluated with respect to the catalyst, silane, solvent, reaction conditions, and substrates.
- Hoffmann, Marcel,Deshmukh, Sunetra,Werner, Thomas
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p. 4532 - 4543
(2015/07/27)
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- (2-Arylethenyl)-1,3,5-triazin-2-amines as a novel histamine H4 receptor ligands
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Within the constantly growing number of histamine H4 (H4R) receptor ligands there is a large group of azine derivatives. A series of novel compounds in the group of 4-methylpiperazine-1,3,5-triazine-2-amines were designed and obtained. Considered structures were modified at the triazine 6-position by introduction of variously substituted arylethenyl moieties. Their affinities to histamine H4 receptors were evaluated in radioligand binding assays with use of Sf9 cells, transiently expressing human H4R. Pharmacological studies results allowed to identify 4-[(E)-2-(3-chlorophenyl)ethenyl]-6-(4-methylpiperazin-1-yl)-1,3,5-triazin-2-amine (Ki Combining double low line 253 nM) as the most potent compound in the present series.
- Kamińska, Katarzyna,Ziemba, Julia,Ner, Joanna,Schwed, Johannes Stephan,?azewska, Dorota,Wi?cek, Ma?gorzata,Karcz, Tadeusz,Olejarz, Agnieszka,Latacz, Gniewomir,Kuder, Kamil,Kottke, Tim,Zygmunt, Ma?gorzata,Sapa, Jacek,Karolak-Wojciechowska, Janina,Stark, Holger,Kie?-Kononowicz, Katarzyna
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p. 238 - 251
(2015/09/22)
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- Synthesis of [N,P] ligands based on pyrrole. Application to the total synthesis of arnottin i
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This paper describes the synthesis of a new class of [N,P] ligands based on pyrrole with a dimethylamino group as hard donor and a phosphine moiety as soft base. We have also modified the phosphine fragment to change the electronic and steric properties of these ligands. Palladium complex 3a proved to be very efficient in Heck cross-coupling reactions and in intramolecular aryl-aryl couplings of esters and amides. We have demonstrated the applicability and efficiency of this novel catalyst in the total synthesis of the natural product arnottin I.
- Suárez-Meneses, Jesús V.,Bonilla-Reyes, Edgar,Blé-González, Ever A.,Ortega-Alfaro, M. Carmen,Toscano, Rubén Alfredo,Cordero-Vargas, Alejandro,López-Cortés, José G.
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supporting information
p. 1422 - 1430
(2014/02/14)
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- Phosphine-catalyzed domino reactions: A route to functionalized bicyclic skeletons
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A novel strategy that involves phosphine-catalyzed sequential [2+3] and [3+2] annulation reactions was developed. In this domino reaction, γ-substituted allenoates were used as novel C4 synthons, and the bicyclic cyclopenta[b]dihydrofuran derivatives were produced in good to excellent diastereoselectivities and yields under mild conditions. Furthermore, preliminary studies on an asymmetric variant of this reaction proceeded with moderate enantioselectivity.
- Li, Erqing,Huang, You
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supporting information
p. 3520 - 3527
(2014/04/03)
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- A bifunctional palladated rasta resin for Mizoroki-Heck reactions
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Bifunctional palladated rasta resins 2b and 2c bearing both phosphino and basic amino groups have been successfully used for Mizoroki-Heck reactions between aryl iodides and alkenes without adding a soluble base. We have also shown that 2c can be easily regenerated after reaction and reused. To the best of our knowledge, this work represents the first use of a bifunctional palladated polymer for a CC bond forming reaction.
- Derible, Antoine,Yang, Yun-Chin,Toy, Patrick H.,Becht, Jean-Michel,Le Drian, Claude
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p. 4331 - 4333
(2014/07/22)
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- Nano Pd-Fe3O4@Alg beads: As an efficient and magnetically separable catalyst for Suzuki, Heck and Buchwald-Hartwig coupling reactions
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Catalytic processes are the backbone of many chemical industries. In a comparative study of various heterogeneous catalytic systems, we report efficient and magnetically separable nano Pd-Fe3O4@Alg beads as catalysts for Suzuki, Heck and Buchwald-Hartwig coupling reactions. This catalyst was characterized by SEM, TEM, HRTEM, XRD, EDAX, FT-IR, VSM, DSC-TGA, BET, and UV-Visible spectroscopy. This heterogeneous catalyst showed high catalytic activity and stability for C-C and C-N bond forming coupling reactions with excellent product yield under ligand free conditions. The beads of nano Pd-Fe3O4@Alg can be separated from the reaction mixture by an external magnet and reused for several successive cycles with no appreciable loss in the catalytic activity. The Suzuki and Heck coupling reactions in aqueous medium are greener routes, which is an added advantage of this protocol. This journal is
- Shelkar, Radheshyam S.,Gund, Sitaram H.,Nagarkar, Jayashree M.
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p. 53387 - 53396
(2015/02/05)
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- Multifunctional cyclodextrin-based N,N-bidentate ligands for aqueous Heck arylation
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Novel Pd(II) complexes coordinated by N,N-bidentate ligands derived from cyclodextrins have been synthesized by copper-catalyzed azide alkyne 1,3-cycloaddition (CuAAC). Depending on the nature of the N,N-bidentate ligand, fast or slow equilibriums between the free N,N-bidentate ligand and the Pd-species were detected by NMR measurements. The new Pd(II) complexes acted as efficient water soluble catalysts for the Heck reaction of aryl iodides in aqueous medium. The reaction could tolerate aerobic conditions and affords the coupling products in good yields. Once the reaction was complete, the product and the catalyst could be recovered separately by simple decantation.
- Potier, Jonathan,Menuel, Stéphane,Rousseau, Jolanta,Tumkevicius, Sigitas,Hapiot, Frédéric,Monflier, Eric
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- Versatile palladium-catalyzed C-H olefination of (hetero)arenes at room temperature
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The room-temperature oxidative C-H/C-H cross-couplings between (hetero)arenes and alkenes, coumarins or quinones have been reported by using a highly electrophilic palladium species [Pd(TFA)2], generated in situ from Pd(OAc)2and TFA, as the catalyst and cheap (NH4)2S2O8as the oxidant under air.
- She, Zhijie,Shi, Yang,Huang, Yumin,Cheng, Yangyang,Song, Feijie,You, Jingsong
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supporting information
p. 13914 - 13916
(2015/01/09)
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- Multicomponent, flow diazotization/mizoroki-heck coupling protocol: Dispelling myths about working with diazonium salts
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A single pass flow diazotization/Mizoroki-Heck protocol has been developed for the production of cinnimoyl and styryl products. The factors that govern aryl diazonium salt stability have been examined in detail leading to the development of a MeOH/DMF co-solvent system in which the diazonium salts can be generated in the presence of all other reaction components and then coupled selectively to give the desired products. Finally the key role of the reaction quench for flow reactions has been demonstrated.
- Nalivela, Kumara S.,Tilley, Michael,McGuire, Michael A.,Organ, Michael G.
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supporting information
p. 6603 - 6607
(2014/06/09)
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- Phosphine-functionalized magnetic nanoparticles (PFMN) as a magnetic recyclable phosphorus ligand: Preparation of its palladium(II) complex for Heck reaction of chloroarenes
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In this study, magnetic nanoparticles (MNs) were functionalized using chlorodiphenylphosphine (ClPPh2) and phosphine-functionalized magnetic nanoparticles (PFMN) as a recyclable phosphorus ligand was obtained. Also, palladium(II) complex of PFMN ligand (Pd-PFMN) was prepared and its catalytic activity was evaluated in the Heck reaction of chloroarenes. The results revealed that, this new catalyst showed high catalytic activity in the Heck reaction of chloroarenes and this can be attributed to the high reactivity of Pd complex involving phosphorus ligands and dispersible ability of MNs in solution as a high surface area support.
- Khalafi-Nezhad, Ali,Panahi, Farhad
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- PHENYLALKYL SULFAMATE COMPOUND AND MUSCLE RELAXANT COMPOSITION COMPRISING THE SAME
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The present invention relates to novel phenylalkyl sulfamate compounds, a method for preventing or treating a disease associated with muscle spasm. The present invention ensures the enhancement of muscle relaxation activity essential for alleviation of muscle spasm, such that it is promising for preventing or treating various diseases associated with muscle spasm.
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Page/Page column 27-28; 41-42
(2014/01/08)
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- Pd(II)-catalyzed oxidative Heck-type reaction of triarylphosphines with alkenes via carbon-phosphorus bond cleavage
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A Pd(II)-catalyzed oxidative Heck-type reaction of triarylphosphines with alkenes via carbon-phosphorus bond cleavage was reported. Under the optimal reaction conditions, most reactions proceeded smoothly to give the expected coupling products in acceptable to high yields.
- Ma, Ming-Tao,Lu, Jian-Mei
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p. 2102 - 2106
(2013/03/13)
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