- Photoredox/nickel-catalyzed hydroacylation of ethylene with aromatic acids
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We report a general, practical and scalable hydroacylation reaction of ethylene with aromatic carboxylic acids with the synergistic combination of nickel and photoredox catalysis. Under ambient temperature and pressure, feedstock chemicals such as ethylene can be converted into high-value-added aromatic ketones in moderate to good yields (up to 92%) with reaction time of 2-6 hours.
- Chen, Shuai,He, Hengchi,Li, Weipeng,Xie, Jin,Zhang, Lili,Zhu, Chengjian
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supporting information
p. 9064 - 9067
(2021/09/15)
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- Nickel-Mediated Enantiospecific Silylation via Benzylic C-OMe Bond Cleavage
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Benzylic stereocenters are found in bioactive and drug molecules, as enantiopure benzylic alcohols have been used to build such a stereogenic center, but are limited to the construction of a C-C bond. Silylation of alkyl alcohols has the potential to build bioactive molecules and building blocks; however, the development of such a process is challenging and unknown. Herein, we describe an unprecedented AgF-assisted nickel catalysis in the enantiospecific silylation of benzylic ethers.
- Balakrishnan, Venkadesh,Murugesan, Vetrivelan,Chindan, Bincy,Rasappan, Ramesh
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p. 1333 - 1338
(2021/02/20)
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- SUBSTITUTED DIHYDROPYRAZOLO PYRAZINE CARBOXAMIDE DERIVATIVES
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The invention relates to substituted dihydropyrazolo pyrazine carboxamide derivatives and to processes for their preparation, and also to their use for preparing medicaments for the treatment and/or prophylaxis of diseases, in particular cardiovascular disorders, preferably thrombotic or thromboembolic disorders, and diabetes, and also urogenital and ophthalmic disorders.
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- Ligand-Controlled Chemoselective C(acyl)-O Bond vs C(aryl)-C Bond Activation of Aromatic Esters in Nickel Catalyzed C(sp2)-C(sp3) Cross-Couplings
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A ligand-controlled and site-selective nickel catalyzed Suzuki-Miyaura cross-coupling reaction with aromatic esters and alkyl organoboron reagents as coupling partners was developed. This methodology provides a facile route for C(sp2)-C(sp3) bond formation in a straightforward fashion by successful suppression of the undesired β-hydride elimination process. By simply switching the phosphorus ligand, the ester substrates are converted into the alkylated arenes and ketone products, respectively. The utility of this newly developed protocol was demonstrated by its wide substrate scope, broad functional group tolerance and application in the synthesis of key intermediates for the synthesis of bioactive compounds. DFT studies on the oxidative addition step helped rationalizing this intriguing reaction chemoselectivity: whereas nickel complexes with bidentate ligands favor the C(aryl)-C bond cleavage in the oxidative addition step leading to the alkylated product via a decarbonylative process, nickel complexes with monodentate phosphorus ligands favor activation of the C(acyl)-O bond, which later generates the ketone product.
- Chatupheeraphat, Adisak,Liao, Hsuan-Hung,Srimontree, Watchara,Guo, Lin,Minenkov, Yury,Poater, Albert,Cavallo, Luigi,Rueping, Magnus
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supporting information
p. 3724 - 3735
(2018/03/21)
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- Isomerization of Allylic Alcohols to Ketones Catalyzed by Well-Defined Iron PNP Pincer Catalysts
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[Fe(PNP)(CO)HCl] (PNP=di-(2-diisopropylphosphanyl-ethyl)amine), activated in situ with KOtBu, is a highly active catalyst for the isomerization of allylic alcohols to ketones without an external hydrogen supply. High reaction rates were obtained at 80 °C, but the catalyst is also sufficiently active at room temperature with most substrates. The reaction follows a self-hydrogen-borrowing mechanism, as verified by DFT calculations. An alternative isomerization through alkene insertion and β-hydride elimination could be excluded on the basis of a much higher barrier. In alcoholic solvents, the ketone product is further reduced to the saturated alcohol.
- Xia, Tian,Wei, Zhihong,Spiegelberg, Brian,Jiao, Haijun,Hinze, Sandra,de Vries, Johannes G.
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supporting information
p. 4043 - 4049
(2018/01/27)
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- Stereoselective Ketone Rearrangements with Hypervalent Iodine Reagents
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The first stereoselective version of an iodine(III)-mediated rearrangement of arylketones in the presence of orthoesters is described. The reaction products, α-arylated esters, are very useful intermediates in the synthesis of bioactive compounds such as ibuprofen. With chiral lactic acid-based iodine(III) reagents product selectivities of up to 73 % ee have been achieved.
- Malmedy, Florence,Wirth, Thomas
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supporting information
p. 16072 - 16077
(2016/10/30)
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- Transition-Metal-Free Self-Hydrogen-Transferring Allylic Isomerization
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Phenanthroline and tert-butoxide have been established as powerful radical initiators in reactions such as the SRN1-type coupling reactions due to the cooperation of large heteroarenes and a special feature of tert-butoxide. The first phenanthroline-tert-butoxide-catalyzed transition-metal-free allylic isomerization is described. The resulting ketones are key intermediates for indenes. The control experiments rule out the base-promoted allylic anion pathway. The radical pathway is supported by experimental evidence that includes kinetic study, kinetic isotope effect, isotope-labeling experiments, trapping experiments, and EPR experiments.
- Zheng, Hong-Xing,Xiao, Zu-Feng,Yao, Chuan-Zhi,Li, Qiang-Qiang,Ning, Xiao-Shan,Kang, Yan-Biao,Tang, Yong
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p. 6102 - 6105
(2016/01/09)
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- Highly chemoselective and versatile method for direct conversion of carboxylic acids to ketones utilizing zinc Ate complexes
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Various carboxylic acids were directly transformed into the corresponding ketones by utilizing organozinc ate complexes, which provide high chemoselectivity without any overreaction to the undesired tertiary carbinol, owing to formation of a stable tetrahedral zincioketal intermediate. This method offers good overall atom/step/pot economy and operational simplicity. No need to overreact: Various carboxylic acids were directly transformed to the corresponding ketones by utilizing organozinc ate complexes, which provide high chemoselectivity without any overreaction to undesired tertiary carbinol, owing to formation of a stable tetrahedral zincioketal intermediate. This method offers good overall atom/step/pot economy and operational simplicity.
- Murata, Ryo,Hirano, Keiichi,Uchiyama, Masanobu
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supporting information
p. 1286 - 1290
(2015/06/08)
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- Direct conversion of allyl arenes to aryl ethylketones via a TBHP-mediated palladium-catalyzed tandem isomerization-Wacker oxidation of terminal alkenes
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A TBHP-mediated palladium-catalyzed tandem isomerization-Wacker oxidation of terminal alkenes was developed. This methodology provides a new efficient and simple route for conversion of a range of allyl arenes directly into aryl ethylketones in good yields with high chemoselectivity.
- Zhao, Jinwu,Liu, Li,Xiang, Shijian,Liu, Qiang,Chen, Huoji
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supporting information
p. 5613 - 5616
(2015/05/27)
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- Ruthenium-catalyzed tandem-isomerization/asymmetric transfer hydrogenation of allylic alcohols
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A one-pot procedure for the direct conversion of racemic allylic alcohols to enantiomerically enriched saturated alcohols is presented. The tandem-isomerization/ asymmetric transfer hydrogenation process is efficiently catalyzed by [{Ru(p-cymene)Cl2}2] in combination with the a-amino acid hydroxyamide ligand 1, and performed under mild conditions in a mixture of ethanol and THF. The saturated alcohol products are isolated in good to excellent chemical yields and in enantiomeric excess up to 93%.
- Slagbrand, Tove,Lundberg, Helena,Adolfsson, Hans
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p. 16102 - 16106
(2015/01/09)
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- DMF as carbon source: Rh-catalyzed α-methylation of ketones
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An unprecedented Rh-catalyzed direct methylation of ketones with N,N-dimethylformamide (DMF) is disclosed. The reaction shows a broad substrate scope, tolerating both aryl and alkyl ketones with various substituents. Mechanistic studies suggest that DMF delivers a methylene fragment followed by a hydride in the methylation process.
- Li, Yang,Xue, Dong,Lu, Wei,Wang, Chao,Liu, Zhao-Tie,Xiao, Jianliang
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supporting information
p. 66 - 69
(2014/01/23)
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- Catalytic isomerization of allylic alcohols promoted by complexes [RuCl2(η6-arene)(PTA-Me)] under homogeneous conditions and supported on Montmorillonite K-10
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The mononuclear arene-ruthenium(II) derivatives [RuCl2(η 6-arene)(PTA-Me)] (arene = C6H6 (3a), p-cymene (3b), 1,3,5-C6H3Me3 (3c), C6Me 6 (3d)), containing the ionic phosphine ligand 1-methyl-3,5-diaza-1- azonia-7-phosphaadamantane chloride (PTA-Me), have been synthesized and fully characterized. These complexes were evaluated as potential catalysts for the redox isomerization of allylic alcohols. Among them, best results in terms of activity were obtained with complex [RuCl2(η6-C 6H6)(PTA-Me)] (3a) which, in combination with K 2CO3 (2.5 equiv. per Ru), was able to selectively isomerize a number of allylic alcohols RCH(OH)CHCH2 (R = H, aryl, alkyl or heteroaryl group) into the corresponding carbonyl compounds RC(O)CH2CH3 in refluxing THF (TOF values up to 800 h -1). Complex [RuCl2(η6-C6H 6)(PTA-Me)] (3a) was adsorbed onto the Montmorillonite K-10 clay, and the resulting solid proved also active in the isomerization of the model substrate 1-octen-3-ol. In addition, it could be easily separated from the reaction media by simple filtration and reused several times (up to 11 consecutive runs) with retention of its efficiency.
- Menéndez-Rodríguez, Lucía,Crochet, Pascale,Cadierno, Victorio
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p. 390 - 399
(2013/02/21)
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- Kinetic resolution of aryl alkenylcarbinols catalyzed by Fc-PIP
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An effective kinetic resolution of a variety of aryl alkenylcarbinols catalyzed by nonenzymatic acyl transfer catalyst Fc-PIP was developed, affording corresponding unreacted alcohols in good to excellent ee value up to 99% and with selectivity factors up to 24.
- Hu, Bin,Meng, Meng,Jiang, Shanshan,Deng, Weiping
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p. 1289 - 1294
(2012/08/28)
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- HYDROXYBUPROPION ANALOGUES FOR TREATING DRUG DEPENDENCE
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The invention provides hydroxybupropion analogues capable of inhibiting the reuptake of one or more monoamines and/or acting as antagonists at nicotinic acetylcholine receptors. The compounds may selectively bind to one or more monoamine transporters, including those for dopamine, norepinephrine, and serotonin and/or may selectively bind to one or more nicotinic acetylcholine receptor subtypes. Such compounds may be used to treat conditions that are responsive to modification of monoamine levels and/or antagonism of nicotinic acetylcholine receptors, including drug dependency, depression, and obesity.
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Page/Page column 67-68
(2011/12/04)
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- COMPOUNDS AND METHODS FOR TREATING RESPIRATORY DISEASES
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Described herein are compounds and compositions, and methods for using the compounds and compositions, for treating respiratory diseases and illness, such as severe acute respiratory syndrome (SARS).
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Page/Page column 26
(2011/11/12)
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- Transformation of α-substituted propanols into γ-amino alcohols through nickel-catalyzed amination on the terminal γ-carbon of propanols
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A nickel-phosphine complex was found to be effective as the catalyst for the transformation of alcohols into β-enaminones, which was successively converted into γ-amino alcohols by a conventional reductant. The sequential transformation is equivalent to the carbon-nitrogen bond formation at the γ-position of saturated alcohols. Georg Thieme Verlag Stuttgart · New York.
- Ueno, Satoshi,Usui, Kazumi,Kuwano, Ryoichi
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supporting information; experimental part
p. 1303 - 1307
(2011/07/08)
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- Synthesis and characterization of in vitro and in vivo profiles of hydroxybupropion analogues: Aids to smoking cessation
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To create potentially superior aids to smoking cessation and/or antidepressants and to elucidate bupropions possible mechanisms of action(s), 23 analogues based on its active hydroxymetabolite (2S,3S)-4a were synthesized and tested for their abilities to inhibit monoamine uptake and nAChR subtype activities in vitro and acute effects of nicotine in vivo. The 3′,4′-dichlorophenyl [(±)-4n], naphthyl (4r), and 3-chlorophenyl or 3-propyl analogues 4s and 4t, respectively, had higher inhibitory potency and/or absolute selectivity than (2S,3S)-4a for inhibition of DA, NE, or 5HT uptake. The 3′-fluorophenyl, 3′-bromophenyl, and 4-biphenyl analogues 4c, 4d, and 4l, respectively, had higher potency for antagonism of α4β2-nAChR than (2S,3S)-4a. Several analogues also had higher potency than (2S,3S)-4a as antagonists of nicotine-mediated antinociception in the tail-flick assay. The results suggest that compounds acting via some combination of DA, NE, or 5HT inhibition and/or antagonism of α4β2-nAChR can potentially be new pharmacotherapeutics for treatment of nicotine dependence.
- Lukas, Ronald J.,Muresan, Ana Z.,Damaj, M. Imad,Blough, Bruce E.,Huang, Xiaodong,Navarro, Hernán A.,Mascarella, S. Wayne,Eaton, J. Brek,Marxer-Miller, Syndia K.,Carroll, F. Ivy
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experimental part
p. 4731 - 4748
(2010/10/03)
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- Efficient synthesis of alkyl aryl ketones & ketals via palladium-catalyzed regioselective arylation of vinyl ethers
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The combination of Pd(OAc)2 with 1,3-bis(diphenylphosphino) propane (dppp) in ethylene glycol constitutes a high-performance catalytic system for highly regioselective arylation of a range of electron-rich vinyl ethers by aryl bromides to provide, upon hydrolysis, alkyl aryl ketones and cyclic ketals in good yields with up to 3.75 × 105 TON and 15625 h-1 TOF.
- Liu, Mingcui,Hyder, Zeynab,Sun, Yawei,Tang, Weijun,Xu, Lijin,Xiao, Jianliang
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supporting information; experimental part
p. 2012 - 2015
(2010/07/04)
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- N, N′-dioxide-Cu(OTf)2 complex catalyzed highly enantioselective amination reaction of N-acetyl enamide
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The N,N′-dioxide-Cu(OTf)2 complexes were applied in the asymmetric amination reaction of N-acetyl enamides with dialkyl azodicarboxylate, giving the corresponding products in good yields with high enantioselectivities (up to 91% ee). Precursors of vicinal diamine were readily obtained with excellent diastereoselectivities (>95:5) by NaBH4 reduction.
- Chang, Lu,Kuang, Yulong,Qin, Bo,Zhou, Xin,Liu, Xiaohua,Lin, Lili,Feng, Xiaoming
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supporting information; scheme or table
p. 2214 - 2217
(2010/08/06)
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- Structure-based design, synthesis, and biological evaluation of a series of novel and reversible inhibitors for the severe acute respiratory syndrome - Coronavirus papain-like protease
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We describe here the design, synthesis, molecular modeling, and biological evaluation of a series of small molecule, nonpeptide inhibitors of SARS-CoV PLpro. Our initial lead compound was identified via high-throughput screening of a diverse chemical library. We subsequently carried out structure - activity relationship studies and optimized the lead structure to potent inhibitors that have shown antiviral activity against SARS-CoV infected Vero E6 cells. Upon the basis of the X-ray crystal structure of inhibitor 24-bound to SARS-CoV PLpro, a drug design template was created. Our structure-based modification led to the design of a more potent inhibitor, 2 (enzyme IC50 = 0.46 μM; antiviral EC50 = 6 μM). Interestingly, its methylamine derivative, 49, displayed good enzyme inhibitory potency (IC50 = 1.3 μM) and the most potent SARS antiviral activity (EC50 = 5.2 μM) in the series. We have carried out computational docking studies and generated a predictive 3D-QSAR model for SARS-CoV PLpro inhibitors.
- Ghosh, Arun K.,Takayama, Jun,Aubin, Yoann,Ratia, Kiira,Chaudhuri, Rima,Baez, Yahira,Sleeman, Katrina,Coughlin, Melissa,Nichols, Daniel B.,Mulhearn, Debbie C.,Prabhakar, Bellur S.,Baker, Susan C.,Johnson, Michael E.,Mesecar, Andrew D.
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experimental part
p. 5228 - 5240
(2010/03/04)
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- Hydrogen-bond-directed catalysis: Faster, regioselective and cleaner heck arylation of electron-rich olefins in alcohols
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A general method for the regioselective Heck reaction of electronrich olefins is presented. Fast, highly regioselective Pd-catalysed α-arylation of electron-rich olefins, vinyl ethers (1a-d), hydroxyl vinyl ethers (1e,f), enamides (1g,h) and a substituted vinyl ether (1i) has been accomplished with a diverse range of aryl bromides (2a-r), for the first time, in cheap, green and easily available alcohols with no need for any halide scavengers or salt additives. The reaction proceeds with high efficiency, leading exclusively to the a-products, in 2-propanol and particularly in ethylene glycol. In the latter, the arylation can be catalysed at a palladium loading of 0.1 mol% and finish in as short a time as 0.5 h. The remarkable performance of the alcohol solvents in promoting a regiocontrol is attributed to their hydrogen-bond- donating capability, which is believed to facilitate the dissociation of halide anions from PdII, and hence, the generation of a key ionic Pd II-olefin intermediate responsible for the a product. This belief is further strengthened by the study of a benchmark arylation reaction in 21 different solvents. The study revealed that exclusive α-regioselective arylation takes place in almost all of the protic solvents, and there is a rough correlation between the α-arylation rates and the solvent parameter ETN. The method is simpler, cleaner and more general than those established thus far.
- Hyder, Zeynab,Ruan, Jiwu,Xiao, Jianliang
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experimental part
p. 5555 - 5566
(2009/06/17)
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- Pentamethylcyclopentadienyl ruthenium: an efficient catalyst for the redox isomerization of functionalized allylic alcohols into carbonyl compounds
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The catalytic activity of the ruthenium(II) complex [RuCp*(CH3CN)3][PF6] 1 in the transposition of allylic alcohols into carbonyl compounds, in acetonitrile, is reported. This catalyst has proven to be able to catalyze the transformation of poorly reactive and/or functionalized substrates under smooth conditions.
- Bouziane, Asmae,Carboni, Bertrand,Bruneau, Christian,Carreaux, Fran?ois,Renaud, Jean-Luc
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experimental part
p. 11745 - 11750
(2009/04/11)
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- Unexpected formation of aryl ketones by palladium-catalyzed coupling of aryl bromides with vinylic acetates
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A palladium-catalyzed coupling reaction of aryl bromides with vinylic acetates in the presence of tributyitin methoxide has been described. Unexpected formation of aryl ketones was obtained. Preliminary mechanistic studies indicated that the reaction proceeded by the addition of the aryl moiety in the coordination sphere of palladium to a ketene.
- Jean, Mickael,Renaulty, Jacques,Uriac, Philippe,Capet, Marc,Van De Weghe, Pierre
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p. 3623 - 3625
(2008/02/12)
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- DIHYDROIMIDAZOTHIAZOLE DERIVATIVES
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Compounds of formula (I): or pharmaceutically acceptable salts thereof, exhibit 5-HT1A agonism in addition to noradrenaline reuptake inhibition and optionally also 5-HT reuptake inhibition are useful for the treatment of obesity.
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Page/Page column 18
(2008/06/13)
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- PHENYLNAPHTHYLIMIDAZOLES FOR USE ON COPPER SURFACES DURING SOLDERING
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A surface treating agent containing a novel phenylnaphthylimidazole compound represented by the following formula is brought into contact with the surface of copper or a copper alloy. In the formula, when A1 is a phenyl group, then A2 represents a 1-naphthyl group or a 2-naphthyl group, and when A1 is a 1-naphthyl group or a 2-naphthyl group, then A2 represents a phenyl group; and R represents a hydrogen atom or a methyl group.
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Page/Page column 22-23
(2010/02/15)
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- Solid state cleavage of oximes with potassium permanganate supported on alumina
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A manipulatively simple and rapid method for conversion of oximes to the corresponding carbonyl compounds is described. The reaction is conducted under solvent-less conditions using alumina-supported permanganate. According to the reaction system and conditions used, different ketones and aldehydes are obtained in moderate and good yields.
- Imanzadeh,Hajipour,Mallakpour
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p. 735 - 740
(2007/10/03)
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- ALPHA-KETOAMIDE DERIVATIVES
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The invention relates to α-ketoamides of the general formula wherein R 1to R 12have the significances given in the description, and their salts. The α-ketoamide derivatives provided by the present invention inhibit proteinases of viral origin, such as HCV protease, and can be used in the treatment of viral infections, especially viral infections caused by hepatitis C, hepatitis G and human GB viruses.
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- DIRECTION OF ACYLATION OF NAPHTHALENE BY THE FRIEDEL-CRAFTS METHOD
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The Friedel-Crafts acylation of naphthalene by the halides of substituted and unsubstituted aliphatic carboxylic acids with various chain lengths (C2-C6) and various degrees of branching in the hydrocarbon chain was investigated.The effect of the solvent on the direction of acylation shows up during acylation by the least hindered acylating agents (acetyl chloride, acetyl bromide, chloroacetyl chloride, and bromoacetyl bromide).The α isomer is obtained preferentially in chloroform and the β isomer in nitrobenzene.With increase in the length and degree of branching of the hydrocarbon chain the β position of the naphthalene ring becomes the preferred direction of acylation.The main factor which determines the direction of Friedel-Crafts acylation in naphthalene is the steric factor.
- Dumpis, M. A.,Kudryashova, N. I.,Khromov-Borisov, N. V.
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p. 1799 - 1803
(2007/10/02)
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