- Hydrazine-Free Facile Synthesis of Palladium-Tetrakis(Triphenylphosphine)
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We present an easy and very efficient procedure for the synthesis of Pd(PPh3)4 using nontoxic reducing agents. The complex is obtained in a remarkable 83 % yield, and the method can be scaled up. A very detailed spectroscopic and spectrometric characterization is reported.
- Carrasco, Sergio,Martín-Matute, Belén
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- MECHANISM OF ACETYLENE AND OLEFIN INSERTION INTO PALLADIUM-CARBON sigma BONDS.
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The intramolecular acetylene insertion reactions of C1L//2PdCO//2(CH//2)//nC EQUVLNT CCH//3 (1a, L equals Ph//3P, n equals 2; 1b, L equals p-tol//3P, n equals 2; 2, L equals Ph//3P, n equals 3) and the intramolecular olefin insertion reaction of C1L//2PdCO//2CH//2CH//2CH equals CH//2 (3, L equals Ph//3P) have been investigated. The acetylene insertion reactions give stable vinyl complexes 5a, 5b, and 6; the olefin insertion reaction gives an unsaturated lactone by beta -hydrogen elimination from the initially formed insertion product. Kinetic and **3**1P NMR studies show that, as predicted by Thorn and Hoffmann, the reactions proceed by a four-coordinate mechanism, with the triple or double bond displacing a phosphine ligand in a rapidly maintained equilibrium prior to insertion. The triple bond in 2, with the longer carbon chain, is more easily coordinated than that in 1a but inserts less rapidly after coordination.
- Samsel,Norton
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- Synthesis and nicotinic acetylcholine-binding properties of epibatidine homologues: Homoepibatidine and dihomoepibatidine
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Homoepibatidine 2 and dihomoepibatidine 3 have been synthesised from the 8-azabicyclo[3.2.1]oct-6-ene 8 and the 9-azabicyclo[4.2.1]oct-7-ene 9, respectively, the key precursors for reductive Heck coupling reactions. Alternative routes starting from cyclohepta- and cycloocta-1,3-diene are described; deoxygenation of tropane and homotropane epoxides provides a convenient route to 8 and 9. The enantiomers of 2 show similar potency at nicotinic receptors to the corresponding epibatidine enantiomers; the affinity of 3 is lower.
- Malpass,Hemmings,Wallis,Fletcher,Patel
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- Fluoride-catalyzed reduction of palladium(II) to palladium(0)-phosphine complexes
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We demonstrate that in the presence of water and excess PPh3, fluoride ion catalyzes the reduction of (Ph3P)2PdCl 2 under mild conditions to Pd(PPh3)4 in good yields. The inactivation of catalytic F- by formation of highly stable HF2-, and other polyhydrogen fluorides that can form in the reaction, is prevented by adding a strong nonionic base such as P(MeNCH2CH2)3N.
- McLaughlin, Patrick A.,Verkade, John G.
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- Evidence of the formation of zerovalent palladium from Pd(OAc)2 and triphenylphosphine
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The mixture Pd(OAc)2 + nPPh3 (n ≥ 2) and the complex Pd(OAc)2(PPh3)2 commonly used as catalysts in reactions involving aryl and vinyl halides, aryl inflates or allylic acetates spontaneously generate a zerovalent palladium complex that reacts with iodobenzene. Triphenylphosphine reduces the divalent palladium from the complex Pd(OAc)2(PPh3)2 by an intramolecular reaction and is oxidized to triphenylphosphine oxide. In the presence of an excess of triphenylphosphine, the zerovalent palladium complex generated in situ has the same 31P NMR and cyclic voltammetry properties as those of Pd0(PPh3)4.
- Amatore, Christian,Jutand, Anny,M'Barki, Mohamed Amine
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- Reductive elimination from metal phosphonate complexes: Circumvention of competing protonolysis reactions
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The formation of MeP(O)(OPh)2 by reductive elimination from L2PdMe(P(O)(OPh)2) species has been investigated. The electronic and steric effects of the supporting ligands were investigated by studying reductive elimination reactions from a series of discrete complexes containing nitrogen- and phosphorus-based ligands. The P(O)-C(sp3) bond-forming reaction is slow when the intermediate species contains bidentate nitrogen ligands or small basic monodentate phosphines. Analogous complexes bearing large bite angle diphosphines such as dppf and Xantphos undergo reductive elimination at ambient temperature. The rate of MeP(O)(OPh)2 formation by reductive elimination from (dppf)PdMe(P(O)(OPh)2) is not affected by the identity or concentration of added ligand (excess dppf or PPh3), suggesting that the reductive elimination occurs from a four- or three-coordinate intermediate. When the rate of reductive elimination is slow, protonolysis reactions between L2PdMe(P(O)(OPh)2) intermediates and HP(O)(OPh)2 leads to the formation of bis-phosphonate complexes. The protonolysis reaction can be circumvented by the use of large bite angle phosphines such as dppf and Xantphos, which lead to rapid rates of P(O)-C(sp3) bond formation. These results demonstrate that the formation of P(O)-C(sp3) bonds by reductive elimination from L2PdRP(O)(OR)2 complexes is quite sensitive to the steric bulk of the supporting ligand and the presence of excess hydrogen phosphonate.
- Stockland Jr., Robert A.,Levine, Adam M.,Giovine, Matthew T.,Guzei, Ilia A.,Cannistra, Joseph C.
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- Synthesis, biological activity and molecular modeling of new biphenylic carboxamides as potent and selective CB2 receptor ligands
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The CB2 receptor is a therapeutic target of increasing importance for several diseases, including pain, inflammation, neurodegeneration, cancer and osteoporosis. While several compounds showing CB2-selective agonist or inverse agonist properties have been developed, only few CB2 receptor selective neutral antagonists are actually known. Such type of compounds could be useful to study more in depth the role of the CB2 receptor, because they lack the ability to counteract its g €constitutiveg € activity. Here we describe the synthesis and biological activity of a series of biphenylic carboxamides as a new class of CB2 receptor selective ligands. In binding assays, one of these compounds showed good CB2 receptor affinity and selectivity (Ki Combining double low line 11.48 nM; Selectivity Index Combining double low line 130). Furthermore, in functional assays, the same compound showed a very interesting pharmacological profile as CB2 receptor selective neutral antagonist. These results pave the way to further developments, including structural optimization, with the aim to obtain more potent CB2 receptor ligands with this peculiar feature.
- Bertini, Simone,Parkkari, Teija,Savinainen, Juha R.,Arena, Chiara,Saccomanni, Giuseppe,Saguto, Simone,Ligresti, Alessia,Allarà, Marco,Bruno, Agostino,Marinelli, Luciana,Di Marzo, Vincenzo,Novellino, Ettore,Manera, Clementina,Macchia, Marco
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- Three-Coordinate Pd(0) with Rare-Earth Metalloligands: Synergetic CO Activation and Double P-C Bond Cleavage-Formation Reactions
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Metalation of β-diketiminato rare-earth metal complexes LnacnacLn(PhNCH2PPh2)2 (Ln = Y, Yb, Lu) with (COD)Pd(CH2SiMe3)2 afforded three-coordinate Pd(0) complexes supported by two sterically less bulky phosphines and a Pd → Ln dative interaction. The Pd(0) center is prone to ligation with isonitrile and CO; in the latter case, the insertion of a second CO with the Y-N bond was assisted via a precoordination of CO on the Pd(0) center, which led to the formation of an anionic Pd(0) carbamoyl. The reaction of the Pd-Y complex with iodobenzene showed a remarkable double P-C bond cleavage-formation pathway within the heterobimetallic Pd-Y core to afford (Ph3P)2PdI(Ph), imine PhNCH2, and a β-diketiminato yttrium diiodide. In the related reaction of LnacnacY(PhNCH2PPh2)2 with (Ph3P)2PdI(Ph), the P-C bond cleavage following with a N-C bond formation was observed. Computational studies revealed a synergetic bimetallic mechanism for these reactions.
- Cui, Peng,Wu, Changjiang,Du, Jun,Luo, Gen,Huang, Zeming,Zhou, Shuangliu
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- Palladium-catalysed annulation reaction of allenyltins with β-iodo vinylic acids: Selective synthesis of α-pyrones
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Palladium-catalysed regio- and stereoselective annulation of allenyl stannanes by β-iodo vinylic acids gives the corresponding α-pyrones in high yields. This annulation most probably proceeds through a Stille reaction/cyclisation sequence.
- Rousset,Abarbri,Thibonnet,Duchene,Parrain
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- Cyclopropanation of cyclohexenone by diazomethane catalyzed by palladium diacetate: Evidence for the formation of palladium(0) nanoparticles
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The diazomethane-mediated cyclopropanation of cyclohexenone using Pd(OAc)2 and different sources of Pd(0) species as precatalysts has been studied. In the presence of an excess of diazomethane, Pd-(OAc)2 rapidly evolves to the formation of palladium nanoparticles (less than 1 min), which are active as catalysts in the cyclopropanation process. The nature of these particles has been analyzed through transmission electron microscopy showing a size distribution between 6 and 40 nm. These nanoparticles generated in situ are more active man Pd(0) complexes, preformed nanoparticles, and commercial palladium powder. Cyclic voltammetry measurements of the reaction solution after completion show the presence of Pd(0) species. This is the first time that Pd(0) nanoparticles are evidenced in a cyclopropanation reaction. Moreover, the reduction of Pd(OAc)2 to Pd(0) in the presence of diazomethane has been theoretically studied through density functional calculations. The formation of methyl and allyl acetates as organic byproducts has been predicted by the theoretical calculations, and these species, as well as oligomers derived from them, have been detected by spectrometric and spectroscopic techniques (MS, NMR, and IR).
- Illa, Ona,Rodriguez-Garcia, Cristobal,Acosta-Silva, Carles,Favier, Isabelle,Picurelli, David,Oliva, Antonio,Gomez, Montserrat,Branchadell, Vicenc,Ortuno, Rosa M.
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- Dimetallic Complexes with Bridging Seven-membered Cycloolefins. Synthesis, Multinuclear NMR.-Spectroscopic Properties and Structure
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The synthesis of dimetallic olefin complexes of the type L1M1C7H7M2L2 (M1=Fe, Co, Rh; M2=Rh, Ir, Pd; L1=CO, C5H5; L2=diene, allyl, P(OR)3) is described.The fluxional structures were investigated by 13C-, 57Fe- and 103Rh-NMR.-spectroscopy, and a cisoid dimetallic coordination, including a (metal, metal)-bond, can be deduced for the C7H7-ring. 57Fe- and 103Rh-chemical shifts give indications for the charge distribution in the 34e-complexes.The homo-dimetallic complex (Cp)Rh(tropone)Rh(Cp) (13, Cp=cyclopentadienyl) and the corresponding 2-methoxytropone complex 14 were synthesized in addition to the above mentioned complexes.A fluxional bis(1-3-ν-allyl)-coordination of the two Rh-atoms was derived from the temperature-dependent 13C-NMR.-spectra.A spin simulation of the (Cp)-multiplets of 12 and 13 yields information about (Rh,Rh)-spin-coupling which amounts to ca. 5 Hz at 30 deg.
- Salzer, Albrecht,Egolf, Thomas,Philipsborn, Wolfgang von
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- Marked effects of azulenyl vs. naphthyl groups on donor-π-acceptor-π-donor small molecules for organic photovoltaic cells
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Although the unique electronic and optical properties of azulene, the azulene-containing organic photovoltaic (OPV) materials have sporadically reported. Here, eight donor-π-acceptor-π-donor conjugated OPV materials entailing guaiazulene or naphthalene as electron donor unit were synthesized and characterized. The azulenyl and naphthyl groups have significant influences on their molecular properties and photovoltaic performances. Compared to naphthalene derivatives, azulene derivatives exhibit red-shifted and wider absorption spectra. However, naphthalene derivatives exhibit much deeper highest occupied molecular orbital (HOMO) energy levels, higher hole mobility and better film morphology, remarkably resulting in approximately 2–4 times higher photovoltaic efficiencies than azulene derivatives.
- Chen, Yao,Huang, Yan,Liu, Jueshan,Lu, Zhiyun,Pang, Zhenguo,Wu, Jianglin,Yang, Lin,Zhao, Suling,Zhu, Youqin
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- Structure-based design, synthesis and anticancer effect of cyclic Smac–polyarginine peptides
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The second mitochondria-derived activator of caspase (Smac/DIABLO) is a pro-apoptotic protein that released from mitochondria into the cytosol when cells undergo apoptosis. Smac promotes caspase activation by binding the inhibitors of apoptosis proteins (IAP), particularly XIAP and eliminating their inhibitory activity. Although the seven N-terminal amino acids AVPIAQK (SmacN7) of Smac protein is able to elicit an anticancer response by itself, it is neither cell-permeable nor stable in the cellular environment. Thus, the use of SmacN7 derivatives and mimetics is an alluring field for cancer therapy. In this study, heptamer Smac peptide was fused to a well-known octaarginine cell-penetrating peptide for promoting its intracellular access. Both therapeutic Smac part and cell-penetrating octaarginine parts of the peptide sequence constrained in a cyclic structure so as to enhance the apoptosis-inducing potential of the SmacN7 peptide. Biological assays interestingly showed that cyclic peptides P4, P5 and P7 gave rise to a significant level of cytotoxicity and apoptosis mediated cell death in multiple myeloma tumor cells (MM) comparing to linear peptide.
- Khalily, Melek Parlak,Gerek?i, Selin,Güle?, Ezgi A.,?zen, Can,?z?ubuk?u, Salih
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- Method for synthesizing tetrakis(triphenylphosphine)palladium by liquid-phase crystallization and application of tetrakis(triphenylphosphine)palladium in emamectin benzoate production
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The invention relates to a method for synthesizing tetrakis(triphenylphosphine)palladium through liquid-phase crystallization and application of tetrakis(triphenylphosphine)palladium in emamectin benzoate production. The method for synthesizing tetrakis(triphenylphosphine)palladium through liquid-phase crystallization comprises the steps of 1, placing DMF in a reactor, adding palladium chloride and triphenylphosphine into the reactor, introducing N2 for protection, and conducting oil bath heating to the temperature of 140-160 DEG C for backflow; 2, dropwise adding hydrazine hydrate into the solution obtained after the reaction in the step 2, controlling the dropwise adding speed, ensuring that the temperature is reduced to 110-140 DEG C after dropwise adding is completed, then naturally cooling to the temperature of 20-40 DEG C, and separating out green crystals; 3, carrying out suction filtration under the protection of N2 to obtain a wet crystal with DMF; 4, leaching the wet crystalobtained in the step 3 by using petroleum ether under the protection of N2, and airing to obtain tetrakis(triphenylphosphine)palladium; and 5, sub-packaging the prepared tetrakis(triphenylphosphine)palladium for later use. The process disclosed by the invention has the advantages of environmental protection, high efficiency, high product purity, easiness in storage and the like.
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Paragraph 0024-0026
(2021/04/03)
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- Modification on the 1,2-dihydro-2-oxo-pyridine-3-carboxamide core to obtain multi-target modulators of endocannabinoid system
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Several preclinical evidence indicate that the modulation of the endocannabinoid system (ECS) represents a promising therapeutic approach for different diseases. However, only few modulators of this system have reached so far an advanced stage of clinical development, mainly due to limited efficacy and CB1 receptor-dependent side effects. Those limitations might be overcome by multi-target compounds that exert pro-cannabinoid activities through the modulation of two or more targets in the ECS. This approach can offer a safer and more effective pharmacological strategy as compared to the modulation of a single target. In this work, we report the synthesis and biological characterization of new 6-aryl-1,2-dihydro-2-oxo-pyridine-3-carboxamide derivatives. Our results identified several compounds exhibiting interesting multi-target profiles within the ECS. In particular, compound B1 showed moderate-to-high affinity for cannabinoid receptors (Ki CB1R = 304 nM, partial agonist, Ki CB2R = 3.1 nM, inverse agonist) and a potent inhibition of AEA uptake (IC50 = 62 nM) with moderate inhibition of FAAH (IC50 = 2.9 μM). The corresponding 2-alkoxypyridine analogue B14 exhibited significant inhibitor activity on both FAAH (IC50 = 69 nM) and AEA uptake (IC50 = 76 nM) without significantly binding to both cannabinoid receptor subtypes. Molecular docking analysis was carried out on the three-dimensional structures of CB1R and CB2R and of FAAH to rationalize the structure-activity relationships of this series of compounds.
- Gado, Francesca,Arena, Chiara,Fauci, Cristiana La,Reynoso-Moreno, Ines,Bertini, Simone,Digiacomo, Maria,Meini, Serena,Poli, Giulio,Macchia, Marco,Tuccinardi, Tiziano,Gertsch, Jürg,Chicca, Andrea,Manera, Clementina
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- One-Pot Two-Step Synthesis of Isochromene-Fused CF3-Substituted Pyrazoles
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An efficient one-pot, two step method for fusing two biologically active motifs, CF3-substituted pyrazoles and isochromenes, was developed. Selective O-benzylation of CF3-substituted pyrazolones and subsequent Pd-catalyzed direct C–H arylation generate a fused tricycle. For the synthesized compounds through-space 13C–19F spin–spin coupling was revealed. In addition, the synthesis of three thioisochromene analogues, and one isocoumarin derivative, was accomplished.
- Nikoli?, Andrea M.,?ivkovi?, Filip,Selakovi?, ?ivota,Wipf, Peter,Opsenica, Igor M.
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supporting information
p. 5616 - 5619
(2020/08/17)
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- METHOD FOR THE PRODUCTION OF TETRAKIS(TRIHYDROCARBYL PHOSPHANE)PALLADIUM(0)
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Method for the production of tetrakis(trihydrocarbylphosphane)palladium(0) in organic solvent, whereby 50 to 100% by weight of the organic solvent consist of at least one polar-aprotic solvent, characterised in that a) at least one palladium compound selected from the group consisting of palladium(II) compounds and palladium(IV) compounds that are soluble in the organic solvent is reacted with b) at least one base, selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal-C1-C4-alcoholates, ammonium carbonate, ammonium hydrogen carbonate, alkaline earth metal hydroxides, alkaline earth metal carbonates, alkaline earth metal hydrogen carbonates, alkaline earth metal-C1-C4-alcoholates, and alkylamines with a total of 2 to 12 carbon atoms; c) at least one trihydrocarbylphosphane; and d) at least one organic reducing agent that is different from the remaining components that are used in the method.
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Paragraph 0038-0050
(2019/07/10)
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- METHODS FOR PRECISION THERAPEUTIC TARGETING OF HUMAN CANCER CELL MOTILITY AND KITS THEREOF
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Disclosed are methods for identifying an agent of interest that alters binding or activity of a client protein to a chaperone and kits thereof.
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Page/Page column 53; 54
(2019/08/29)
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- Conjugated polymer containing pyrene-pyridine groups and synthesis method and application thereof
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The invention discloses a conjugated polymer containing pyrene-pyridine groups as well as a synthesis method and application of the conjugated polymer. The conjugated polymer is shown as a formula I or a formula II, according to the synthesis method, a pyrene derivative and 2, 6-di (acetenyl) pyridine are used as monomers, and the conjugated polymer is synthesized through a Sonogashira condensation polymerization reaction. A method for preparing nanoparticles comprises the following steps: dissolving the conjugated polymer in a volatile solvent to obtain a conjugated polymer solution with theconcentration of 60-125ppm; and adding the conjugated polymer solution into a surfactant solution, carrying out ultrasonic treatment until the solution is clear, and filtering to obtain the product. The conjugated polymer belongs to a low polymer, is small in size and can be used for preparing nanoparticles with the particle size of less than 10nm; the average particle size of the obtained nano particles is smaller than 10 nm, and the nano particles are applied to the fields of metal ions, small organic molecules and cell imaging, so that the detection limit and sensitivity of a detection method are improved.
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Paragraph 0057-0058
(2019/12/25)
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- Method for preparing palladium (0) or platinum (0) composite compound from triphenylphosphine
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The invention provides a method for preparing a palladium (0) or platinum (0) composite compound from triphenylphosphine; with use of palladium chloride (PdCl2) or hydrochloroplatinic acid (H2PtCl6.xH2O) as a starting material, preliminary preparation reaction is not needed, and commercially purchased palladium chloride or hydrochloroplatinic acid can be directly used for reaction. The reaction process is simple, all the reactions are carried out in a same reactor, separation of intermediate products is not needed, and the loss is reduced; the yield of target products is high; the recovery problem of reaction residues is simplified. The product has high reactivity and catalytic activity in various reactions, and has broad application prospects.
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Paragraph 0032
(2019/01/08)
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- Precision therapeutic targeting of human cancer cell motility
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Increased cancer cell motility constitutes a root cause of end organ destruction and mortality, but its complex regulation represents a barrier to precision targeting. We use the unique characteristics of small molecules to probe and selectively modulate cell motility. By coupling efficient chemical synthesis routes to multiple upfront in parallel phenotypic screens, we identify that KBU2046 inhibits cell motility and cell invasion in vitro. Across three different murine models of human prostate and breast cancer, KBU2046 inhibits metastasis, decreases bone destruction, and prolongs survival at nanomolar blood concentrations after oral administration. Comprehensive molecular, cellular and systemic-level assays all support a high level of selectivity. KBU2046 binds chaperone heterocomplexes, selectively alters binding of client proteins that regulate motility, and lacks all the hallmarks of classical chaperone inhibitors, including toxicity. We identify a unique cell motility regulatory mechanism and synthesize a targeted therapeutic, providing a platform to pursue studies in humans.
- Xu, Li,Gordon, Ryan,Farmer, Rebecca,Pattanayak, Abhinandan,Binkowski, Andrew,Huang, Xiaoke,Avram, Michael,Krishna, Sankar,Voll, Eric,Pavese, Janet,Chavez, Juan,Bruce, James,Mazar, Andrew,Nibbs, Antoinette,Anderson, Wayne,Li, Lin,Jovanovic, Borko,Pruell, Sean,Valsecchi, Matias,Francia, Giulio,Betori, Rick,Scheidt, Karl,Bergan, Raymond
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- A synthesis method according to sets up qu tan hydrobromide
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The invention discloses a synthesis method of eletriptan hydrobromate, which comprises the following steps: reacting (R)-1-acetyl-3-(N-methylpyrrolidinyl-2-methy)-5-bromo-1H-indole and metal in an organic solvent to form a metal complex, reacting the metal complex with a boron reagent in an organic solvent to form aryl borane or aryl borate, carrying out acid-catalyzed hydrolysis to obtain aryl boric acid, and carrying out coupling and hydrolysis on the aryl boric acid and 2-chloroethylphenyl sulfone under the actions of a catalyst and an alkali to obtain eletriptan, or directly carrying out coupling and hydrolysis on the metal complex and 2-chloroethylphenyl sulfone to obtain eletriptan; and carrying out salification on the eletriptan and hydrobromic acid in an organic solvent to finally obtain the eletriptan hydrobromate. The method is simple to operate, has the advantages of high safety, high stability, low cost and higher yield, and is suitable for industrial production.
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Paragraph 0055-0056
(2017/10/22)
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- Asymmetric octafluorocyclopentene compound with continuous selectivity for Hg2+ and Cys, preparation method and application thereof
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The invention discloses [1-[2-methyl-3-benzothiophene], 2-(2-methyl-5-(4-phenyl)-(2-benzoylquinoline-8-benzothiazolyl)-3-thienyl)] octafluorocyclopentene, a preparation method and an application thereof. The preparation method comprises the following steps: by taking benzothiophene as a raw material, replacing by methyl iodide and bromizing and then reacting with octafluorocyclopentene, thereby generating mono-substituted octafluorocyclopentene; by taking 2-thiotolene as a raw material, bromizing and causing n-butyllithium to react with tributyl borate; connecting aldehyde-terminated benzene with thiophene ring through Stuzki coupling; protecting by adopting ethylene glycol and then reacting with the mono-substituted octafluorocyclopentene; reducing into alcoholic hydroxyl group and becoming methylene-containing bromine; reacting with 8-hydroxyquinoline-2-aldehyde group; and finally reacting with 2-amino thiophenol, thereby acquiring a target compound. The compound prepared according to the invention can be used for continuously detecting specific ions and amino acid and has an excellent selectivity.
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Paragraph 0016; 0042
(2017/07/20)
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- Comprising benzimidazole group of asymmetric perfluoro pentene photochromic fluorescent probe compound and its preparation method and application
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The invention discloses an asymmetric perfluorocyclopentene photochromic fluorescent probe compound containing a benzimidazole group as well as a preparation method and an application of the asymmetric perfluorocyclopentene photochromic fluorescent probe compound. The photochromic material can keep good photochromic performance in a solution and a crystalline phase, has excellent performance such as good chemical and thermal stability, remarkable fatigue resistance, relatively high cyclizing quantum yield, relatively strong fluorescence property and very good sensitivity in an open loop state and a closed loop state in the solution, can be used for high-density holographic optical storage with storage attribute comparable with that of rewritable photon type storage and an symmetric type perfluorocyclopentene material, is relatively low in cost in preparation material and relatively great in application prospect.
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Paragraph 0039; 0040
(2017/08/25)
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- INHIBITION OF CANCER CELL MOTILITY
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Provided herein are compositions and methods for inhibiting cancer cell motility and/or metastasis. In particular embodiments, KBU2046 (or an analog thereof) and one or more additional therapies (e.g., cancer therapies (e.g., hormone therapies and chemotherapies) are provided to inhibit cancer cell motility, inhibit metastasis, and/or treat cancer (e.g., prostate cancer, lung cancer, breast cancer, colon cancer, etc.).
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Page/Page column 40; 41
(2016/06/01)
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- A method for preparing abiraterone acetate (by machine translation)
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The invention relates to a method for preparing abiraterone acetate, the method is to dehydrogenation epandrosterone as raw materials, with hydrazine hydrate, iodine response, to obtain 17-iodo-androst -5,16-diene -3 β-ol, then the under the catalysis of palladium benzene phosphine base43 with 3-pyridine zinc halide occurs arab League bit dragon Negishi coupling reaction, the final with acetyl chloride or acetic anhydride esterification, to obtain the target product abiraterone acetate. (by machine translation)
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Paragraph 0036; 0037
(2017/02/09)
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- Kinetics and mechanisms of homogeneous catalytic reactions. Part 12. Hydroalcoxycarbonylation of 1-hexene using palladium/triphenylphosphine systems as catalyst precursors
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Systems prepared in situ by addition of n equivalents of triphenylphosphine to palladium dichloride in the presence of m equivalents of para-toluenesulfonic acid (TSA), PdCl2/nPPh3/mTSA (n and m varying between 2 and 10), were used as precatalysts for the olefin carbonylation (1-hexene, cyclohexene and styrene) with alcohols (MeOH, EtOH, n-PrOH and i-PrOH) to generate the corresponding esters (hydroalcoxycarbonylation), under mild reaction conditions. For 1-hexene carbonylation in presence of methanol (1-hexene hydromethoxycarbonylation), the most active system was PdCl2/6PPh3/5TSA at P(CO) = 50 atm and T = 125°C, which was also active for the hydromethoxycarbonylation of other olefins (1-hexene > styrene > cyclohexene). This system was regioselective towards the linear product for 1-hexene and towards the branched product for styrene. A kinetic study of 1-hexene hydromethoxycarbonylation catalyzed by PdCl2/6PPh3/5TSA showed that the initial reaction rate (ro) was first order on Pd and MeOH concentrations and fractional order with respect to CO concentration; for olefin concentration was found a saturation curve. These kinetic results, together with coordination chemistry and computational DFT studies, allow us to propose a catalytic cycle involving species of the type [Pd(H)(L)(PPh3)2]+n (L = Cl, n = 0; L = CO, MeOH, olefin and PPh3, n = 1) as the catalytically active species and three sequential reactions: (1) olefin insertion into the Pd-H bond to yield Pd-alkyl species, (2) CO insertion into the Pd-C bond to generate Pd-acyl intermediates, and (3) the methanolysis of Pd-acyl species to produce the corresponding methyl esters, regenerate the active species and restart the cycle; the last reaction is considered the rate-determining step (rds) of the mechanism.
- Rosales, Merln,Pacheco, Ins,Medina, Jairo,Fernndez, Juan,Gonzlez, ngel,Izquierdo, Rodolfo,Melean, Luis G.,Baricelli, Pablo J.
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p. 1717 - 1727
(2015/02/19)
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- Pyridonaphthyridine PI3K/MTOR Dual Inhibitors and Preparation and Use Thereof
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The present invention relates to a pyridonaphthyridine compound as represented by general formula (I), which has a dual PI3K and mTOR inhibition effect, and its pharmaceutically acceptable salt, stereoisomer and deuteride thereof, wherein R1, R2, R3, R4, R5, R6, R7 and X are as defined in the specification; the present invention also relates to a method for preparing said compound, a pharmaceutical composition and a pharmaceutical formulation containing said compound, and uses of said compound in treating and/or preventing a proliferative disease and in the manufacture of a medicament for treating and/or preventing a proliferative disease.
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(2014/04/17)
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- LINEAR PYRIDAZINE AND PYRROLE COMPOUNDS, METHOD FOR OBTAINING THEM AND APPLICATIONS
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The present invention relates to linear pyridazine compounds, and more particularly to those of these compounds which are oligopyridazine compounds, to processes for obtaining them, to their uses, and also to their reduction to pyrroles and to the uses of the pyrrole, pyridazinylpyrrole and oligopyrrole compounds obtained. The invention relates in particular to the uses as medicaments, in particular for treating pathologies such as cancer, bacterial infections or parasitic infections, and also the applications in the materials, environmental, electronics and optics field.
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Page/Page column 32
(2010/02/16)
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- Organometallic complexes of palladium (II) derived from 2,6-diacetylpyridine dimethylketal
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PdCl2 reacts with 2,6-diacetylpyridine(dap) (1:1) in refluxing MeOH to give the pincer complex [Pd(O1,N1,C 1-L)Cl](1) and (QH)2[{PdCl2(μ-Cl)}]2 (2), where L is the monoanionic ligand resulting from deprotonation of the acetyl methyl group of the monoketal of dap and QH is C5H 3NH{C-(OMe)Me}2-2,6, the diketal of Hdap+. Reaction of 2 with NEt3 (1:2) in MeOH affords Q = C5H 3N{C(OMe)2Me}2-2,6(3). Complex 1 reacts with 2 equiv of RNC at 0 °C to give trans-[Pd(C1-L)Cl(CNR) 2](R = Xy = 2,6-dimethylphenyl(4a), tBu (4b)) but at room temperature affords [Pd(O2, C2-LR)Cl(CNR)](R = Xy (5a), tBu(5b)). The ligand LR results from the insertion of one isocyanide into the Pd-C bond plus a tautomerization process from η-ketoimine to β-ketoenamine and coordinates in 5 through the carbonyl oxygen atom (O2) and the inserted isocyanide carbon atom (C2). The reaction of 1 with 1 equiv of RNC at 0 °C leads to a mixture of [Pd (N1,C1-L)Cl(CNR)] (R = Xy (6a), tBu (6b); 85-90%), 1, and 4, but at room temperature gives the pincer complex [Pd (O1,N1,C2-LR)Cl] (R = Xy (7a), tBu (7b)), resulting from insertion/tautomerization processes similar to that leading to 5. Complex 7 reacts at 0 °C (1) with 2 equiv of RNC to give trans-[Pd (C2-LR)Cl (CNXy) 2] (R = Xy (8a), tBu (8b)) or (2) with 1 equiv of tBuNC to afford 5b. The reaction of 1 (1) with [Tl(acac)] gives [Pd(N1,C1-L)(acac)] (9); (2) with chelating ligands N ∧N affords [Pd(C1-L)Cl(N∧N)](N ∧N = 2,2'-bipyridine = bpy (10), 4,4'-di-tert-butyl-2,2'- bipyridine = dbbpy (11)); (3) with 1 equiv of PPh3 gives, in the same way as with isocyanides, an equilibrium mixture of [Pd(N1,C 1-L)Cl(PPh3)] (12), 1, and trans-[Pd(C1-L)Cl (PPh3)2](13), which is the only product when 2 equiv of PPh3 is added to the reaction mixture; and(4) with excess PPh 3 affords the monoketal of dap, C5H3N{C(O)Me-2} {C(OMe)2Me-6}(14), and [Pd(PPh3)4]. The crystal structures of complexes 1, 2, 5b, 6a, and 7a have been determined.
- Vicente, Jose,Arcas, Aurelia,Julia-Hernandez, Francisco,Bautista, Delia,Jones, Peter G.
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p. 3066 - 3076
(2010/10/04)
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- Purine compounds
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The invention provides an antimycobacterial 6-aryl-9-(m- or p-substituted-benzyl) purine and purine analog compounds.
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Page/Page column 23; 25
(2010/11/28)
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- METAL COMPOUND AND PREPARATION METHOD THEREFOR
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The invention concerns the preparation of a metal chelate, in particular a precious metal β-diketonate or a precious metal phosphine complex MLaXb, where M is a metal atom, L is a ligand, X is an anion which is preferably a halide, HCO3ˉ, NO3ˉ, CO32é or carboxylate, a is a number equal to or less than the coordination number of the metal, b is 0, 1, 2 or 3, comprising reacting an ammine compound of metal M with a complexing compound, which is preferably a phosphine or a diketonate. Metal compounds which can be made by this process are also described.
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Page/Page column 5
(2010/11/26)
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- Interaction of PdCl2-2-(β-diphenylphosphine)ethylpyridine complex with diols and CO: Synthesis of new alkoxycarbonyl complexes, key intermediates to cyclic carbonates
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PdCl2PN (PN = 2-(β-diphenylphosphine)ethylpyridine) was found to be effective in the promotion of the alkoxycarbonylation of diols [(1,2-hydroxyethane (HE); 1,2- and 1,3-hydroxypropane (1,2HP, 1,3HP), 1,2-, 1,3-, and 1,4-hydroxybutane (1,2HB, 1,3HB, 1,4HB)]. The relevant mono-alkoxycarbonyl complexes of the diols, of formula PdClPN(COO-R-OH), were isolated, characterized in solution, and studied for their reactivity. All complexes in the presence of different reagents release the alkoxycarbonyl group directly as cyclic carbonate or as chloroformate, which "in situ" converts into cyclic carbonate or other valuable carbonyl products. The structure of the complexes PdCl[(COO-CH2-CH2-CH 2(OH)](PN) (4c) and PdCl(COO-CH2-CH(OH)-C 2H5)(PN) (4d) was also derived by single-crystal X-ray diffraction.
- Giannoccaro, Potenzo,Cornacchia, Daniele,Doronzo, Salvatore,Mesto, Ernesto,Quaranta, Eugenio,Aresta, Michele
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p. 2872 - 2879
(2008/10/09)
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- Coordination chemistry of Ga(C5Me4Ph): Novel homoleptic d10 cluster complexes of palladium
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The synthesis and characterization of the novel sterically encumbered Ga(I) ligand GaCp*Ph (1b) (Cp*Ph = C 5Me4Ph) is presented. GaCp*Ph reacts with the Pd(0) source Pd2(dvds)3 (dvds = tetramethyldivinyldisiloxane) to give the trinuclear cluster [Pd 3(GaCp*Ph)(μ2-GaCp *Ph)(μ3-GaCp*Ph)2(dvds)] (2a). 2a is the first example of a Ga(I)-containing cluster with a potentially labile olefinic ligand. It was found that 2a is an intermediate in the formation of the dinuclear cluster [Pd2(GaCp*Ph) 2(μ2-GaCp*Ph)3] (2b), which is formed on reaction of 2a with GaCp*Ph. Both clusters were found to be labile toward GaCp*, AlCp*, or phosphines, giving substitution products in all cases.
- Buchin, Beatrice,Gemel, Christian,Cadenbach, Thomas,Fischer, Roland A.
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p. 1789 - 1794
(2008/10/09)
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- Synthesis of novel metal-germavinylidene complexes from bisgermavinylidene
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The bisgermavinylidene [(Me3SiN=PPh2) 2C=Ge→Ge=C(PPh2=NSiMe3)2] (1) has been used as the source of unstable germavinylidene for the synthesis of a series of metal-germavinylidene complexes. Treatment of 1 with M(PPh 3)4 (M = Ni, Pd) afforded the metal-germavinylidene complexes [{(Me3SiN=PPh2)2C=Ge} 2Ni(PPh3)2] (2) and [{(Me3SiN= PPh2)2C= Ge-μ2}Pd(PPh3)] 2 (3), respectively. The germavinylidene moiety from 1 acts as a two-electron terminal and bridging ligand, respectively. Similar reaction of 1 with AgCl or Aul gave [(Me3-SiN=PPh2)2C=Ge(Ag) (Cl)]2 (5) and [(Me3SiN=PPh2) 2C=Ge(Au)(I)]2 (6), respectively. The result has shown that the germavinylidene moiety from 1 behaves as a Lewis base and undergoes an insertion reaction into the metal-halogen bond. X-ray structures of 2, 3, 5, and 6 have been determined.
- Leung, Wing-Por,So, Cheuk-Wai,Kan, Kwok-Wai,Chan, Hoi-Shan,Mak, Thomas C. W.
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p. 5033 - 5037
(2008/10/09)
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- Triheterocyclic compounds, compositions, and methods for treating cancer or viral diseases
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The present invention relates to novel Triheterocyclic Compounds, compositions comprising a Triheterocyclic Compound, and methods useful for treating or preventing cancer or a neoplastic disorder comprising administering a Triheterocyclic Compound. The compounds, compositions, and methods of the invention are also useful for inhibiting the growth of a cancer cell or neoplastic cell, treating or preventing a viral infection, or inhibiting the replication and/or infectivity of a virus.
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Page/Page column 46
(2010/02/14)
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- Bis(triphenylphosphine)palladium(II)phthalimide - An easily prepared precatalyst for efficient Suzuki-Miyaura coupling of aryl bromides
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In this paper we report the synthesis and application of a novel palladium(II) complex, bis(triphenylphosphine)palladium(II)phthalimide 1. Its utility in the Suzuki-Miyaura coupling of aryl bromides with a variety of aryl- and heteroarylboronic acids, under relatively mild conditions, is described. Complex 1 is easily prepared from tetrakis(triphenylphosphine)palladium(0) and phthalimide in 78% yield and is air, light and moisture stable. On following the kinetics of the cross-coupling reaction of 4-nitro-1-bromobenzene with phenylboronic acid, mediated by 1 (1 mol%) in THF/aqueous 1 M Na 2CO3 (1/1, v/v) at 60°C, an initial induction period is observed, indicating that 1 is a precatalyst. The described work extends on our recent finding that 'imidate' type ligands have an influence in palladium-catalysed cross-coupling processes.
- Chaignon, Nicholas M.,Fairlamb, Ian J.S.,Kapdi, Anant R.,Taylor, Richard J.K.,Whitwood, Adrian C.
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p. 191 - 199
(2008/10/09)
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- NEW BICYCLIC ANGIOTENSIN II AGONISTS
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There is provided compounds of formula (I), wherein R1a, R1b, n, Y1, Y2, Y3, Y4, Z1, Z2, R2 and R3 have meanings given in the description, and pharmaceutically-acceptable salts thereof, which compounds are useful as selective agonists of the AT2 receptor, and thus, in particular, in the treatment of inter alia gastrointestinal conditions, such as dyspepsia, IBS and MOF, and cardiovascular disorders.
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- Sequential insertion of formaldehyde and carbon monoxide into a sulfide-bridged Pd-Ge bond followed by reductive elimination to form a [1,3,2] oxathiagermolan-4-one
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The reaction of (Et3P)2Pd(μ-S)Ge[N(SiMe 3)2]2 (2) with paraformaldehyde under photolytic conditions results in the insertion of formaldehyde into the Pd-Ge bond, with bond cleavage, to give (Et3P)2Pd(μ-S) (μCH2O)Ge[N(SiMe3)2]2 (3). Subsequent addition of CO to 3 results in migratory insertion into the Pd-C bond, followed by rapid reductive elimination to regenerate the Pd0 metal center and give a unique five-membered organic heterocycle, Ge[N(SiMe 3)2]2-SC(O)CH2O (6). The X-ray crystal structure of the dppe (dppe = bis(diphenylphosphino)-ethane) derivative of 3, (dppe)Pd(μ-S)(μCH2O)Ge[N(SiMe3) 2]2 (4), is reported.
- Cygan, Zuzanna T.,Kampf, Jeff W.,Banaszak Holl, Mark M.
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p. 2370 - 2375
(2008/10/09)
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- PIN1-MODULATING COMPOUNDS AND METHODS OF USE THEREOF
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The invention is directed to modulators, e.g., inhibitors, of Pin 1 and Pin 1-related proteins and the use of such modulators for treatment of Pin 1 associated states, e.g., for the treatment of cancer.
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Page/Page column 195
(2008/06/13)
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- Understanding the coupling of heteroaromatic substrates: Synthesis, structures, and reductive eliminations of heteroarylpalladium amido complexes
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Palladium furyl- and thiophenyl complexes have been studied to uncover the origin of the difference in reactivity between coupling of five-membered heterocyclic halides and coupling of aryl halides and six-membered heteroaryl halides. A range of DPPF-ligated furanylpalladium and thiophenylpalladium halide and amido complexes were synthesized, and several examples were structurally characterized. The heteroatom in the 2-heteroaryl groups did not coordinate palladium to generate η2-heteroaryl complexes. The furyl- and thiophenylpalladium complexes underwent reductive elimination of heteroarylamines in yields that were much different for related 2- and 3-isomers. The yields of reductive elimination from these isomeric complexes paralleled the yields from catalytic aminations of 2- and 3-halofurans and 2- and 3-halothiophenes. This correlation suggests that the scope of the amination of five-membered heteroaryl halides is controlled by the reductive elimination step. The yields of reductive elimination correlated with the distribution of electron density at different positions of furans and thiophenes, and this correlation between electron density at different positions of the heteroarenes explains why yields are higher for reductive elimination from 2-furyl and 3-thiophenyl complexes than they are from 3-furyl and 2-thiophenyl complexes.
- Hooper, Mark W.,Hartwig, John F.
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p. 3394 - 3403
(2008/10/08)
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- Reactivity of [Pd3(μ-OAc)3(μ,η2-MeSCHCO 2Et-C,S)3] in the presence of triphenylphosphine: A model of the early steps of the Pd/PR3-catalysed Heck reaction
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The stable complex [Pd(η1-OAc)(η2-MeSCHCO2Et-C,S)(PPh 3)] (2) is readily formed by addition of triphenylphosphine to [Pd3(μ-OAc)3(μ,η2-MeSCHCO 2Et-C,S)3] (1:1 P:Pd) in acetone. It crystallizes in the monoclinic space group C2/c, with Z=8, a=145.08(2), b=109.82(1), c=306.33(3) pm and β=96.3(1)°, R(F)=0.026, Rw (F2)=0.0765. The coordination of a second triphenylphosphine to the palladium atom leads to [Pd(η1-OAc){CH(SMe)CO2Et}(PPh3) 2] (3). Whereas 2 appears to be remarkably stable, 3, after a slow reductive elimination, evolves mainly to [Pd(η2-MeSCHCO2Et-C,S)(PPh3) 2]-. Zero-valent palladium species can also be generated by electrochemical reduction of 3. The rate constant for the oxidative addition of iodobenzene to the electrogenerated palladium(0) species has been estimated.
- Basato, Marino,Sesto, Barbara,Zecca, Marco,Valle, Giovanni,Antonello, Sabrina,Maran, Flavio
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p. 201 - 210
(2007/10/03)
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- 2,3-substituted pyridines for the treatment of inflammation
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A class of substituted pyridyl compounds is described for use in treating inflammation and inflammation-related disorders. Compounds of particular interest are defined by Formula II wherein R1 is selected from hydrido, halo, alkoxy, haloalkoxy, aryl, alkylthio, alkylamino, aralkoxy, azido and alkenyloxy; wherein R2 is selected from hydrido, cyano, hydroxyalkyl, haloalkyl, aminoalkyl, alkylaminoalkyl, alkylcarbonyloxyalkyl, aminocarbonyl and alkylcarbonylaminoalkyl; and wherein R5 and R6 are one or more radicals independently selected from halo, alkylsulfonyl, aminosulfonyl, alkoxy and alkylthio; provided one of R5 and R6 is substituted with alkylsulfonyl, aminosulfonyl, or haloalkylsulfonyl; or a pharmaceutically-acceptable salt thereof.
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- Methods of receptor modulation and uses therefor
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Receptor modulating agents capable of modulating cell surface receptors by affecting the cell surface receptor trafficking pathway are utilized for the treatment and diagnosis of a variety of disorders in warm-blooded animals, including neoplastic disorders. The receptor modulating agents are comprised of a covalently bound rerouting moiety and targeting moiety.
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- Biotinylated cobalamins
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A biotinylated cobalamin, formed from a vitamin B 12 molecule coupled to a biotin molecule, is disclosed. In a preferred embodiment, the vitamin B 12 molecule is cyanocobalamin. The biotin molecule can also be coupled to a rerouting moiety, optionally through a biotin binding protein such as avidin or streptavidin. The biotinylated cobalamin binds to a cell surface receptor, is invaginated, and once internalized affects the receptor trafficking pathway.
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- Receptor modulating agents
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Receptor modulating agents capable of modulating cell surface receptors by affecting the cell surface receptor trafficking pathway. The receptor modulating agents are comprised of a covalently bound rerouting moiety and targeting moiety.
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- Water soluble vitamin B12 receptor modulating agents and methods related thereto
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Vitamin B12 receptor modulating agents capable of modulating cell surface receptors by affecting the cell surface receptor trafficking pathway are disclosed. The vitamin B12 receptor modulating agents are comprised of a covalently bound rerouting moiety and targeting moiety linked by a water-solublizing linker.
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- Carbon-sulfur bond-forming reductive elimination involving sp-, sp2-, and sp3-hybridized carbon. Mechanism, steric effects, and electronic effects on sulfide formation
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Palladium thiolato complexes [(L)Pd(R)(SR')], within which L is a chelating ligand such as DPPE, DPPP, DPPBz, DPPF, or TRANSPHOS, R is a methyl, alkenyl, aryl, or alkynyl ligand, and R' is an aryl or alkyl group, were synthesized by substitution or proton-transfer reactions. All of these thiolato complexes were found to undergo carbon-sulfur bond-forming inductive elimination in high yields to form dialkyl sulfides, diaryl sulfides, alkyl aryl sulfides, alkyl alkenyl sulfides, and alkyl alkynyl sulfides. Reductive eliminations forming alkenyl alkyl sulfides and aryl alkyl sulfides were the fastest. Eliminations of alkynyl alkyl sulfides were slower, and elimination of dialkyl sulfide was the slowest. Thus the relative rates for sulfide elimination as a function of the hybridization of the palladium-bound carbon follow the trend sp2 > sp >> sp3. Rates of reductive elimination were faster for cis-chelating phosphine ligands with larger bite angles. Kinetic studies, along with results from radical trapping reactions, analysis of solvent effects; and analysis of complexes with chelating phosphines of varying rigidity, were conducted with [Pd(L)(S-tert-butyl)(Ar)] and [Pd(L)(S- tert-butyl)(Me)]. Carbon-sulfur bond-forming reductive eliminations involving both saturated and unsaturated hydrocarbyl groups proceed by an intramolecular, concerted mechanism. Systematic changes in the electronic properties of the thiolate and aryl groups showed that reductive elimination is the fastest for electron deficient aryl groups and electron rich arenethiolates, suggesting that the reaction follows a mechanism in which the thiolate acts as a nucleophile and the aryl group an electrophile. Studies with thiolate ligands and hydrocarbyl ligands of varying steric demands favor a migration mechanism involving coordination of the hydrocarbyl ligand in the transition state.
- Mann, Grace,Baranano, David,Hartwig, John F.,Rheingold, Arnold L.,Guzei, Ilia A.
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p. 9205 - 9219
(2007/10/03)
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- Influence of Water on Catalytic Oxidation of Ph3P and Reduction of Pd(2+) to Pd(0) in the Reaction of Pd(acac)2 and Pd(acac)2 · Ph3P with excess PPh3
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An IR and NMR study showed that Pd(acac)2 · Ph3P does not react with excess Ph3P in anhydrous benzene, and no coordination of additional Ph3P molecules to the metal atom or further transformation of coordinated acetylacetonate ligands takes place. Addition of water favors phosphine coordination and formation of complexes containing two C-bonded acetylacetonate ligands or acetylacetonate anions. When performing the reaction under an inert atmosphere Pd(2+) is reduced to Pd(0), and the complex Pd(PPh3)4 is formed. In presence of oxygen, Ph3P is catalytically oxidized with subsequent regeneration of Pd(acac)2 · Ph3P.
- Tyukalova,Ratovskii,Belykh,Shmidt
-
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- Process for removal of allyl group or allyloxycarbonyl group
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This invention relates to a process for the removal of an allyl or allyloxycarbonyl group from an allyl or allyloxycarbonyl group protected compound (such as an allylic ester, carbonate, carbamate, O-allyl derivatives or N-allyl derivatives), which comprises contacting the allyl or allyloxycarbonyl group protected compound with a sulfinic acid compound, in the presence of a palladium catalyst in a reaction-inert solvent. Preferably, the sulfinic acid compound is represented by the formula: wherein X is C1-20 alkyl, substituted C1-20 alkyl (wherein the substituent(s) are independently halo, nitro, sulfo, oxo, amino, cyano, carboxy, hydroxy or moieties derived therefrom), phenyl, substituted phenyl (wherein the substituent(s) are independently C1-3 alkyl, halo nitro, sulfo, oxo, amino, cyano, carboxy, hydroxy, acetamido or moieties derived therefrom), furyl or thienyl; and M is hydrogen, an alkali metal or ammonium salt residue. Of these, most preferred sulfinic acid compound is lithium p-toluenesulfinate, sodium p-toluenesulfinate, potassium p-toluenesulfinate, p-toluenesulfinic acid, ammonium p-toluenesulfinate, lithium benzenesulfinate, sodium benzenesulfinate, potassium benzenesulfinate, benzenesulfinic acid or ammonium benzenesulfinate. This invention is well suited to a process for the conversion of an allyl ester of 5R,6S-6-(1R-hydroxyethyl)-2-(1R-oxo-3S-thiolanylthio)-2-penem-3-carboxylic acid to 5R,6S-6-(1R-hydroxyethyl)-2-(1R-oxo-3S-thiolanylthio)-2-penem-3-carboxylic acid.
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- 2, 3-substituted pyridines for the treatment of inflammation
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A class of substituted pyridyl compounds is described for use in treating inflammation and inflammation-related disorders. Compounds of particular interest are defined by Formula II STR1 wherein R1 is selected from hydrido, halo, alkoxy, haloalkoxy, aryl, alkylthio, alkylamino, aralkoxy, azido and allyloxy; wherein R2 is selected from hydrido, cyano, hydroxyalkyl, haloalkyl, aminoalkyl, aminocarbonyl and alkylcarbonylaminoalkyl; and wherein R5 and R6 are one or more radicals independently selected from halo, alkylsulfonyl, aminosulfonyl, alkoxy and alkylthio; provided one of R5 and R6 is substituted with alkylsulfonyl, aminosulfonyl, or haloalkylsulfonyl; or a pharmaceutically-acceptable salt thereof.
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- Preparation and palladium-catalysed arylation of indolylzinc halides
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Indolylzinc halides are prepared by two methods: transmetallation of indolyllithiums with zinc chloride and oxidative addition of active zinc to iodoindoles. The palladium-catalysed reaction of the indolylzinc halides provides a practical method for synthesizing arylindoles.
- Sakamoto, Takao,Kondo, Yoshinori,Takazawa, Nobuo,Yamanaka, Hiroshi
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p. 1927 - 1934
(2007/10/03)
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