- Synthesis, characterization, and catalytic activity of a ruthenium carbene complex coordinated with bidentate 2-pyridine-carboxylato ligands
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The halide and phosphine free complex [(sIMes)(C5H 4N-2-CO2)2RuCHPh] (7) (sIMes = 1,3-dimesitylimidazolidin-2-ylidene) bearing two bidentate 2-pyridinecarboxylato ligands was synthesized from the carbene complex [(sIMes)(PCy 3)(Cl)2RuCHPh] (4) and the silver 2-pyridine-carboxylate (8). The molecular structure of the octahedral complex 7 reveals that the two carboxylato functions are coordinated in cis geometry to the ruthenium center. Catalyst 7 exhibits activity in ring-closing metathesis (RCM) reactions after addition of a cocatalyst (HCl) in dichloromethane as well as in methanol solution.
- Hahn, F. Ekkehardt,Paas, Martin,Fr?hlich, Roland
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Read Online
- SUBSTITUENT-INCLUDING UREA COMPOUND
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An object of the present invention is to provide a compound that has a specific chemical structure having an activation effect on SIRT6 and is useful as an active component for preventing and treating inflammatory diseases. The present invention relates to a compound represented by Formula (1) or a pharmaceutically acceptable salt thereof. (Each symbol in Formula (1) has the same definition as that described in the specification.)
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Paragraph 0507; 0534-0536; 0655-0657
(2021/12/03)
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- Preparation method of medical intermediate N-BOC-3-pyrroline
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The invention discloses a preparation method of a medical intermediate N-BOC-3-pyrroline. The method comprises the following steps: adding a proper amount of benzylamine, 3-bromopropylene, dichloromethane and an alkaline reagent into a reaction bottle for reaction to obtain an enamine compound; dissolving the enamine compound in dichloromethane, adding a catalyst (Grubbs first generation) for reaction, adding anhydrous sodium sulfate after adding water for layering, and performing suction filtration to obtain mother liquor; adding 1-chloroethyl chloroformate and methanol into the mother liquor, debenzylating to obtain pink solid, adding petroleum ether into the pink solid, pulping, and carrying out suction filtration to obtain 3-pyrroline hydrochloride; and re-dissolving the 3-pyrroline hydrochloride with water, adding an alkaline solution of NaHCO3 and (BOC)2O, stirring and reacting, extracting after the reaction is finished, separating out an organic phase, and drying to obtain a finished product of N-BOC-3-pyrroline. The method is low in raw material cost, simple in process step, high in yield, small in pollution, high in product purity and suitable for industrial production.
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Paragraph 0065; 0067; 0069; 0071; 0073; 0075
(2021/07/31)
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- Water soluble homogeneous catalysts that are recoverable by phase selectivity and host-guest interactions
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A chemical reaction is catalyzed in an organic solvent using a water soluble N-heterocyclic carbene homogeneous catalyst to form a reaction mixture. An aqueous phase in the reaction mixture. A solvent in which the catalyst is insoluble is added to the reaction mixture, causing the catalyst to migrate to the aqueous phase to form a catalyst-laden aqueous phase. The catalyst is extracted from the catalyst-laden aqueous phase.
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Page/Page column 2
(2020/08/30)
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- A simple and practical preparation of an efficient water soluble olefin metathesis catalyst
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This study details homogeneous olefin metathesis in water catalysed by a di-ammonium functionalised Ru-alkylidene complex. A facile gram scale synthesis of an air stable catalyst precursor which can be readily converted to its water soluble derivative is described. The di-ammonium functionalised Ru-alkylidene complex facilitates a range of ring-closing metathesis (RCM) and cross-metathesis (CM) reactions in water.
- Wang, Zhen J.,Jackson, W. Roy,Robinson, Andrea J.
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supporting information
p. 3407 - 3414
(2015/06/25)
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- Effect of added salt on ring-closing metathesis catalyzed by a water-soluble hoveyda-grubbs type complex to form N-containing heterocycles in aqueous media
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The efficiency of ring-closing metathesis catalyzed by a Hoveyda-Grubbs type catalyst in water can be enhanced by addition of a chloride salt under neutral conditions. UV-vis spectroscopic study showed that a characteristic band of the catalyst around 380 nm remained over 16 h in the presence of KCl, whereas the band distinctly decreased in the absence of KCl. The disappearance of the band is ascribed to a displacement of a chloride ligand by a water molecule or a hydroxide anion. The spectral changes can be related to the metathesis activity. The experimental results indicate that avoidance of the chloride ligand loss is important to maintain the metathesis activity in water.
- Matsuo, Takashi,Yoshida, Takefumi,Fujii, Akira,Kawahara, Keiya,Hirota, Shun
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p. 5313 - 5319
(2013/11/06)
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- Studies of a soluble polyethylene glycol immobilized ruthenium catalyst in aqueous media
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We have developed an air-stable soluble polyethylene glycol bound ruthenium catalyst which performs efficient ring-closing metathesis in organic solvents as well as in aqueous media.
- Zaman, Shazia,Chen, Hongyuan,Abell, Andrew D.
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experimental part
p. 878 - 880
(2011/03/20)
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- COMPOUNDS FOR TREATING DISORDERS MEDIATED BY METABOTROPIC GLUTAMATE RECEPTOR 5, AND METHODS OF USE THEREOF
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Provided herein are compounds and methods of synthesis thereof. The compounds provided herein are useful for the treatment, prevention, and/or management of various disorders, such as neurological disorders, psychiatric disorders, neuromuscular disorders, gastrointestinal disorders, lower urinary tract disorder, and cancer. Compounds provided herein modulate the activity of metabotropic glutamate receptor 5 (mGluR5) in the central nervous system or the periphery. Pharmaceutical formulations containing the compounds and their methods of use are also provided herein.
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Page/Page column 148
(2010/11/03)
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- Design, synthesis, and structure-activity relationships of novel bicyclic azole-amines as negative allosteric modulators of metabotropic glutamate receptor 5
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A novel series of diaryl bicyclic azole-amines that are potent selective negative modulators of metabotropic glutamate receptor 5 (mGluR5) were identified through rational design. An initial hit compound 5a of modest potency (IC50 = 1.2 μM) was synthesized. Evaluation of structure-activity relationships (SAR) on the left-hand side of the molecule revealed a preference for a 2-substituted pyridine group linked directly to the central heterocycle. Variation of the central azolo-amine portion of the molecule revealed a preference for the [4,5-c]-oxazoloazepine scaffold, while right-hand side variants showed a preference for ortho- and meta-substituted benzene rings linked directly to the tertiary amine of the saturated heterocycle. These iterations led to the synthesis of 29b, a potent (IC50 = 16 nM) and selective negative modulator that showed good brain penetrance, high receptor occupancy, and a duration of action greater than 1 h in rat when administered intraperitoneally. Formal PK studies in rat and Rhesus monkey revealed a short half-life that was attributable to high first-pass clearance.
- Burdi, Douglas F.,Hunt, Rachel,Fan, Lei,Hu, Tao,Wang, Jun,Guo, Zihong,Huang, Zhiqiang,Wu, Chengde,Hardy, Larry,Detheux, Michel,Orsini, Michael A.,Quinton, Maria S.,Lew, Robert,Spear, Kerry
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supporting information; experimental part
p. 7107 - 7118
(2010/12/25)
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- Convenient preparation of optically pure 3-aryloxy-pyrrolidines
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Chiral 3-methanesulfonyl-1-Boc-pyrrolidine and piperidine were reacted with sodium phenolates, resulting in a mixture of displacement and elimination products. Following carbamate deprotection and pH adjustment, the 3-pyrroline and tetrahydropyridine by-products resulting from elimination were easily removed through aqueous partitioning and/or concentration. Although the pyrrolidines were formed with a high degree of optical purity, slight racemization was observed for the piperidine case because elevated temperatures were required to effect displacement. Copyright Taylor & Francis Group, LLC.
- Benard, Christophe,Mohammad, Rahim,Saraswat, Neerja,Shan, Rudong,Maiti, Samarendra N.,Wuts, Peter G. M.,Stier, Michael,Lints, Teresa,Bradow, James,Schwarz, Jacob B.
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p. 517 - 524
(2008/04/12)
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- Small-molecule N-heterocyclic-carbene-containing olefin-metathesis catalysts for use in water
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(Chemical Equation Presented) ROMPing around in water: Two well-defined, small-molecule olefin-metathesis catalysts (1 and 2) are introduced. While they are insufficiently stable to mediate most cross-metathesis reactions in water, these catalysts competently mediate ring-opening metathesis polymerization (ROMP) and ring-closing metathesis reactions in an aqueous environment.
- Jordan, Jason P.,Grubbs, Robert H.
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p. 5152 - 5155
(2008/03/14)
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- Salicylaldimine ruthenium alkylidene complexes: Metathesis catalysts tuned for protic solvents
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Tuning the electronic and steric environment of olefin metathesis catalysts with specialized ligands can adapt them to broader applications, including metathesis in aqueous solvents. Bidentate salicylaldimine ligands are known to stabilize ruthenium alkylidene complexes, as well as allow ringclosing metathesis in protic media. Here, we report the synthesis and characterization of exceptionally robust olefin metathesis catalysts bearing both bidentate salicylaldimine and N-heterocyclic carbene ligands, including a trimethylammonium-functionalized complex adapted for polar solvents. NMR spectroscopy and X-ray crystallographic analysis confirm the structures of the complexes. Although the N-heterocyclic carbene-salicylaldimine ligand combination limits the activity of these catalysts in non-polar solvents, this pairing enables efficient ring-closing metathesis of both dienes and enynes in methanol and methanol/water mixtures under air.
- Binder, Joseph B.,Guzei, Ilia A.,Raines, Ronald T.
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p. 395 - 404
(2008/02/07)
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- Olefin metathesis in homogeneous aqueous media catalyzed by conventional ruthenium catalysts
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(Chemical Equation Presented) Olefin metathesis in aqueous solvents is sought for applications in green chemistry and with the hydrophilic substrates of chemical biology, such as proteins and polysaccharides. Most demonstrations of metathesis in water, however, utilize exotic complexes. We have examined the performance of conventional catalysts in homogeneous water/organic mixtures, finding that the second-generation Hoveyda-Grubbs catalyst has extraordinary efficiency in aqueous dimethoxyethane and aqueous acetone. High (71-95%) conversions are achieved for ring-closing and cross metathesis of a variety of substrates in these solvent systems.
- Binder, Joseph B.,Blank, Jacqueline J.,Raines, Ronald T.
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p. 4885 - 4888
(2008/03/14)
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- Highly active water-soluble olefin metathesis catalyst
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A novel water-soluble ruthenium olefin metathesis catalyst supported by a poly(ethylene glycol) conjugated saturated 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene ligand is reported. The catalyst displays improved activity in ring-opening metathesis polymerization, ring-closing metathesis, and cross-metathesis reactions in aqueous media. Copyright
- Hong, Soon Hyeok,Grubbs, Robert H.
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p. 3508 - 3509
(2007/10/03)
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- A solid-supported phosphine-free ruthenium alkylidene for olefin metathesis in methanol and water.
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The synthesis and olefin metathesis activity in protic solvents of 7, a phosphine-free ruthenium alkylidene bound to a hydrophilic solid support are reported. This heterogeneous catalyst promotes relatively efficient ring closing- and cross-metathesis reactions in both methanol and water. The potential utility of homogeneous catalyst 2 for olefin metathesis in methanol is also demonstrated.
- Connon, Stephen J,Blechert, Siegfried
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p. 1873 - 1876
(2007/10/03)
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- Ruthenium carbene complexes with N,N'-bis(mesityl)imidazol-2-ylidene ligands: RCM catalysts of extended scope
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The ruthenium carbene complexes 3a,b bearing imidazol-2-ylidene ligands constitute excellent precatalysts for ring-closing metathesis (RCM) reactions allowing the formation of tri- and tetrasubstituted cycloalkenes. They also apply to annulations that are beyond the scope of the standard Grubbs carbene 1 as well as to ring-closing reactions of acrylic acid derivatives even if the resulting α,β-unsaturated lactones (or lactams) are tri- or tetrasubstituted. The reactivity of 3a was found to be highly dependent on the reaction medium: particularly high reaction rates are observed in toluene, although this solvent also leads to an increased tendency of the catalyst to isomerize the double bonds of the substrates.
- Fuerstner, Alois,Thiel, Oliver R.,Ackermann, Lutz,Schanz, Hans-Joerg,Nolan, Steven P.
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p. 2204 - 2207
(2007/10/03)
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- Ring-closing metathesis in methanol and water
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The ring-closing metathesis (RCM) of acyclic dienes in both methanol and water has been achieved through the use of water-soluble ruthenium alkylidenes. These alkylidenes react readily with acyclic olefins in protic solvents, but they do not cyclize α,ω-dienes because of the instability of the resulting methylidene. Successful cyclization has been achieved through simple substrate modification - incorporation of an olefin substituent allows cyclization to proceed in good yield. A methyl-substituted substrate was cyclized in 60% conversion in methanol, and the incorporation of a phenyl substituent resulted in nearly quantitative cyclization. Phenyl-substituted substrates are best suited for the reaction, as a more stable, active catalyst is regenerated upon each catalyst turnover. Using this methodology, 90% conversion of a water-soluble substrate to a substituted cyclopentene has been achieved in aqueous solution. This methodology has also been successfully applied to increase RCM yield in organic solvents.
- Kirkland, Thomas A.,Lynn, David M.,Grubbs, Robert H.
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p. 9904 - 9909
(2007/10/03)
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- A Convenient Route to 3-Pyrroline Utilizing the Delepine Reaction
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3-Pyrroline(2,5-dihydro-1H-pyrrole) has been prepared from (Z)-1,4-dichloro-2-butene (1) in three steps in an overall yield of 74percent.
- Brandaenge, Svante,Rodriguez, Benito
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p. 347 - 348
(2007/10/02)
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- A New Approach to Allylamines and Pyrrolidines
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The 1,4-adducts 3a-c and 4, readily available from the reaction between diethyl N,N-dichlorophosphoramidate (1) and 1,3-dienes, were found to be convenient precursors for the efficient synthesis of the δ-chloroallylamine hydrochlorides 5a-d and N-phosphorylated allylamines 6a-c and 7.The three-step transformation of 3a-c affords the cis-3,4-dibromopyrrolidine hydrochlorides 10a-c.The preparation of the 2,5-dihydro-1H-pyrrole hydrochlorides 11a-c and trans-3,4-dibromopyrrolidine hydrochlorides 13a-c is also described.The stereochemistry of the reaction is studied.
- Gajda, Tadeusz,Zwierzak, Andrzej
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p. 992 - 1002
(2007/10/02)
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