- Nickel/Cobalt-Catalyzed Reductive Hydrocyanation of Alkynes with Formamide as the Cyano Source, Dehydrant, Reductant, and Solvent
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A Ni/Co co-catalyzed reductive hydrocyanation of various alkynes was developed for the production of saturated nitriles. Hydrocyanic acid is generated in situ from safe and readily available formamide. Formamide played multiple roles as a cyano source, dehydrant, and reductant for the NiII pre-catalyst and vinyl nitriles, along with acting as the co-solvent in this reaction. Detailed mechanistic investigation supported a pathway via hydrocyanation of C≡C bond and the subsequent reduction of C=C bond. Wide substrate scope, the employment of a cheap and stable nickel salt as pre-catalyst, a safe cyano source and convenient experimental operation render this hydrocyanation practical for the laboratory synthesis of saturated nitriles. (Figure presented.).
- Zhang, Jin,Luo, Cui-Ping,Yang, Luo
-
supporting information
p. 283 - 288
(2020/12/01)
-
- Nickel-Catalyzed Markovnikov Transfer Hydrocyanation in the Absence of Lewis Acid
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Hydrocyanation in the absence of toxic HCN gas is highly desirable. Addressing that challenge, transition-metal-catalyzed transfer hydrocyanation using safe HCN precursors has been developed, but these reagents generally require a Lewis acid for activation, and the control of regioselectivity often remains problematic. In this Letter, a Ni-catalyzed highly Markovnikov-selective transfer hydrocyanation that operates in the absence of any Lewis acid is reported. The readily prepared pro-aromatic 1-isopropylcyclohexa-2,5-diene-1-carbonitrile is used as the HCN source, and the reaction shows a broad substrate scope and high functional group tolerance. Terminal styrene derivatives, dienes, and internal alkynes are converted with good to excellent selectivities. Mechanistic studies provide insights into the origin of the regioselectivity.
- Frye, Nils L.,Bhunia, Anup,Studer, Armido
-
supporting information
p. 4456 - 4460
(2020/06/03)
-
- Design, synthesis and biological evaluation of 8-(2-amino-1-hydroxyethyl)-6-hydroxy-1,4-benzoxazine-3(4H)-one derivatives as potent β2-adrenoceptor agonists
-
A series of β2-adrenoceptor agonists with an 8-(2-amino-1-hydroxyethyl)-6-hydroxy-1,4-benzoxazine-3(4H)-one moiety is presented. The stimulatory effects of the compounds on human β2-adrenoceptor and β1-adrenoceptor were characterized by a cell-based assay. Their smooth muscle relaxant activities were tested on isolated guinea pig trachea. Most of the compounds were found to be potent and selective agonists of the β2-adrenoceptor. One of the compounds, (R)-18c, possessed a strong β2-adrenoceptor agonistic effect with an EC50 value of 24 pM. It produced a full and potent airway smooth muscle relaxant effect same as olodaterol. Its onset of action was 3.5 min and its duration of action was more than 12 h in an in vitro guinea pig trachea model of bronchodilation. These results suggest that (R)-18c is a potential candidate for long-acting β2-AR agonists.
- Yi, Ce,Xing, Gang,Wang, Siqi,Li, Xiaoran,Liu, Yichuang,Li, Jinyan,Lin, Bin,Woo, Anthony Yiu-Ho,Zhang, Yuyang,Pan, Li,Cheng, Maosheng
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-
- One-Pot, Tandem Wittig Hydrogenation: Formal C(sp3)-C(sp3) Bond Formation with Extensive Scope
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A one-pot, tandem Wittig hydrogenation of aldehydes with stabilized ylides is reported, representing a formal C(sp3)-C(sp3) bond construction. The tandem reaction operates under mild conditions, is high yielding, and is broad in scope. Chemoselectivity for olefin reduction is observed, and the methodology is demonstrated in the synthesis of lapatinib analogues and a formal synthesis of (±)-cuspareine. Early insights suggest that the chemoselectivity observed in the reduction step is due to partial poisoning of the catalyst, after step one, thus adding to the power of the one-pot procedure.
- Devlin, Rory,Jones, David J.,Mcglacken, Gerard P.
-
supporting information
p. 5223 - 5228
(2020/07/14)
-
- Rhodium-Catalyzed Parallel Kinetic Resolution of Racemic Internal Allenes Towards Enantiopure Allylic 1,3-Diketones
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A rare case of a parallel kinetic resolution of racemic 1,3-disubstituted allenes by means of a rhodium-catalyzed addition to 1,3-diketones furnishing enantiopure allylic 1,3-diketones is described. Mechanistic experiments demonstrate that the different allene enantiomers react in parallel to either the diastereomeric E- or Z-allylic 1,3-diketones with the same absolute configuration of the newly formed stereogenic center. A broad substrate scope demonstrates the synthetic utility of this new method.
- Hilpert, Lukas J.,Breit, Bernhard
-
p. 9939 - 9943
(2019/06/24)
-
- Synthesis of Nitriles from Aldehydes with Elongation of the Molecule with Two Carbon Atoms
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A new protocol for the synthesis of nitriles from carbonyl compounds with elongation of the molecule with two carbon atoms was developed. It involves a reaction of ethyl cyanoacetate with different aldehydes in the presence of iron pentacarbonyl as a redu
- Afanasyev, Oleg I.,Zarochintsev, Alexander,Petrushina, Tatiana,Cherkasova, Anastasia,Denisov, Gleb,Cherkashchenko, Ilia,Chusova, Olga,Jinho, Oh,Man-Seog, Chun,Usanov, Dmitry L.,Semenov, Sergei E.,Chusov, Denis
-
supporting information
p. 32 - 35
(2018/12/05)
-
- Thiocyanate radical mediated dehydration of aldoximes with visible light and air
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We developed a new means of activating aldoximes by an in situ generated thiocyanate radical from ammonium thiocyanate and molecular oxygen at room temperature. With a catalytic amount of organic dye aizenuranine as the photocatalyst, the dehydration of aldoximes proceeds smoothly under visible light irradiation, providing a simple to handle, excellent functional group tolerance, and metal-free protocol for a wide range of nitriles.
- Ban, Yong-Liang,Dai, Jian-Ling,Jin, Xiao-Ling,Zhang, Qing-Bao,Liu, Qiang
-
supporting information
p. 9701 - 9704
(2019/08/15)
-
- A strategy for generating aryl radicals from arylborates through organic photoredox catalysis: Photo-Meerwein type arylation of electron-deficient alkenes
-
Photoinduced reactions of arylboronic acids with electron deficient alkenes under mild organic photoredox catalysis conditions lead to the formation of Meerwein arylation type adducts via the generation of aryl radicals.
- Iwata,Tanaka,Kubosaki,Morita,Yoshimi
-
supporting information
p. 1257 - 1260
(2018/02/09)
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- Cooperative Palladium/Lewis Acid-Catalyzed Transfer Hydrocyanation of Alkenes and Alkynes Using 1-Methylcyclohexa-2,5-diene-1-carbonitrile
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Catalytic transfer hydrocyanation represents a clean and safe alternative to hydrocyanation processes using toxic HCN gas. Such reactions provide access to pharmaceutically important nitrile derivatives starting with alkenes and alkynes. Herein, an efficient and practical cooperative palladium/Lewis acid-catalyzed transfer hydrocyanation of alkenes and alkynes is presented using 1-methylcyclohexa-2,5-diene-1-carbonitrile as a benign and readily available HCN source. A large set of nitrile derivatives (>50 examples) are prepared from both aliphatic and aromatic alkenes with good to excellent anti-Markovnikov selectivity. A range of aliphatic alkenes engage in selective hydrocyanation to provide the corresponding nitriles. The introduced method is useful for chain walking hydrocyanation of internal alkenes to afford terminal nitriles in good regioselectivities. This protocol is also applicable to late-stage modification of bioactive molecules.
- Bhunia, Anup,Bergander, Klaus,Studer, Armido
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supporting information
p. 16353 - 16359
(2018/11/25)
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- Tris(trimethylsilyl)silane-mediated reductive decyanation and cyano transfer reactions of malononitriles
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Reductive decyanation reactions of malononitriles were achieved with tris(trimethylsilyl)silane as a radical mediator. The reaction proceeds via a radical chain mechanism involving a silyl radical addition to the malononitrile to form an imidoyl radical followed by α-cleavage to give a silyl isocyanide and an α-cyano radical. The reaction of a 3-butenyl-substituted malononitrile afforded a decyano/cyanosilylation product in good yield through 1,4-cyano transfer.
- Kawamoto, Takuji,Shimaya, Yudai,Curran, Dennis P.,Kamimura, Akio
-
supporting information
p. 573 - 575
(2018/04/12)
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- Modular radical cross-coupling with sulfones enables access to sp3-rich (fluoro)alkylated scaffolds
-
Cross-coupling chemistry is widely applied to carbon-carbon bond formation in the synthesis of medicines, agrochemicals, and other functional materials. Recently, single-electron-induced variants of this reaction class have proven particularly useful in the formation of C(sp2)-C(sp3) linkages, although certain compound classes have remained a challenge. Here, we report the use of sulfones to activate the alkyl coupling partner in nickel-catalyzed radical cross-coupling with aryl zinc reagents. This method's tolerance of fluoroalkyl substituents proved particularly advantageous for the streamlined preparation of pharmaceutically oriented fluorinated scaffolds that previously required multiple steps, toxic reagents, and nonmodular retrosynthetic blueprints. Five specific sulfone reagents facilitate the rapid assembly of a vast set of compounds, many of which contain challenging fluorination patterns.
- Merchant, Rohan R.,Edwards, Jacob T.,Qin, Tian,Kruszyk, Monika M.,Bi, Cheng,Che, Guanda,Bao, Deng-Hui,Qiao, Wenhua,Sun, Lijie,Collins, Michael R.,Fadeyi, Olugbeminiyi O.,Gallego, Gary M.,Mousseau, James J.,Nuhant, Philippe,Baran, Phil S.
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- Formal reductive addition of acetonitrile to aldehydes and ketones
-
An efficient and highly productive rhodium-catalyzed method for the synthesis of nitriles employing aldehydes or ketones, methyl cyanoacetate, water and carbon monoxide as starting materials has been developed. Simple rhodium chloride without any ligands can be used. The fine tuning of the substrate can lead to the activity higher than 5000 TON.
- Muratov, Karim,Kuchuk, Ekaterina,Vellalath, Sreekumar,Afanasyev, Oleg I.,Moskovets, Alexei P.,Denisov, Gleb,Chusov, Denis
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supporting information
p. 7693 - 7701
(2018/11/02)
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- Process for the Catalytic Reversible Alkene-Nitrile Interconversion
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The present invention refers to processes for catalytic reversible alkene-nitrile interconversion through controllable HCN-free transfer hydrocyanation.
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Page/Page column 20
(2017/09/02)
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- Efficient nickel-catalyzed hydrocyanation of alkenes using acetone cyanohydrin as a safer cyano source
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An active nickel catalyst prepared in situ from a Ni(II) compound, phosphine ligand, and zinc powder was found to be an efficient catalyst system for the hydrocyanation of various alkenes using acetone cyanohydrin as a safer cyano source. The combination of NiCl2·6H2O and 1,3-bis(diphenylphosphino)propane was the most efficient catalyst precursor in DMF. Under the optimized conditions, various styrenes, heterocyclic alkenes, and aliphatic alkenes were converted to their corresponding nitriles in excellent yields.
- Nemoto, Koji,Nagafuchi, Tsuyoshi,Tominaga, Ken-ichi,Sato, Kazuhiko
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p. 3199 - 3203
(2016/07/06)
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- Reductive Transformations of Carbonyl Compounds Catalyzed by Rhodium Supported on a Carbon Matrix by using Carbon Monoxide as a Deoxygenative Agent
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An efficient method for the rhodium on carbon matrix catalyzed preparation of secondary and tertiary amines, cyanoesters, and nitriles through the reductive amination/alkylation of carbonyl compounds was developed, including a convenient procedure for the tandem formal reductive addition of acetonitrile to aldehydes. The catalyst could be reused, and at least three consecutive reaction cycles were performed with comparable efficiency. The method was shown to be compatible with functional groups prone to reduction by hydrogen and complex hydrides. Beyond the matrix: An efficient method for the rhodium on carbon matrix catalyzed preparation of secondary and tertiary amines, cyanoesters, and nitriles through the reductive amination/alkylation of carbonyl compounds is developed, including a convenient procedure for the tandem formal reductive addition of acetonitrile to aldehydes. TON=turnover number.
- Yagafarov, Niyaz Z.,Usanov, Dmitry L.,Moskovets, Alexey P.,Kagramanov, Nikolai D.,Maleev, Victor I.,Chusov, Denis
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p. 2590 - 2593
(2015/09/15)
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- Direct Synthesis of Nitriles from Aldehydes Using an O-Benzoyl Hydroxylamine (BHA) as the Nitrogen Source
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The direct synthesis of nitriles from commercially available or easily prepared aldehydes has been achieved. O-(4-CF3-benzoyl)-hydroxylamine (CF3-BHA) was utilized as the nitrogen source to generate O-acyl oximes in situ with aldehydes, which can be converted to a nitrile with the assistance of a Bronsted acid. Several aliphatic, aromatic, and α,β-unsaturated nitriles that contain different functional groups were prepared in high yields (up to 94% yield). This method has notable advantages, such as simple and mild conditions, high yields, and good functional group tolerance.
- An, Xiao-De,Yu, Shouyun
-
supporting information
p. 5064 - 5067
(2015/11/03)
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- Atom- and step-economical preparation of reduced knoevenagel adducts using CO as a deoxygenative agent
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A highly efficient one-step Rh-catalyzed preparation of reduced Knoevenagel adducts of various aldehydes and ketones with active methylene compounds has been developed. The protocol does not require an external hydrogen source and employs carbon monoxide
- Kolesnikov, Pavel N.,Usanov, Dmitry L.,Barablina, Evgeniya A.,Maleev, Victor I.,Chusov, Denis
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supporting information
p. 5068 - 5071
(2014/12/11)
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- Catalyzation of 1,4-additions of arylboronic acids to α,β- unsaturated substrates using nickel(I) complexes
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Nickel(I) complexes were generated in situ from Ni (PPh3) 2Cl2 using activated iron and the complexes combined with N,N′-bis(4-fluorobenzylidene) ethane-1,2-diamine (BFBED) were then used as a catalyst for the 1,4-addition reaction of arylboronic acids to α,β-unsaturated substrates. The reaction proceeded to completion and did not require the addition of a base but the addition of potassium iodide is crucial to this cross-coupling reaction. Moreover, experimental observations suggested a possible Ni(I)-Ni(III) catalytic cycle mechanism.
- Meng, Jing-Jing,Gao, Min,Dong, Min,Wei, Yu-Ping,Zhang, Wen-Qin
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p. 2107 - 2109
(2014/04/03)
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- Synthesis of alkylated nitriles by [RuHCl(CO)(PPh3) 3]-catalyzed alkylation of acetonitrile using primary alcohols
-
Alkylation reaction of acetonitrile using primary alcohols is effectively catalyzed by [RuHCl(CO)(PPh3)3] in the presence of K 3PO4 as a base. Both benzylic and non-benzylic alcohols coupled with acetonitrile to give alkylated nitriles in good yields.
- Kuwahara, Takashi,Fukuyama, Takahide,Ryu, Ilhyong
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supporting information
p. 1163 - 1165
(2013/10/22)
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- Copper hydride-catalyzed reduction of electron-deficient olefins
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Copper hydride derived from CuF(PPh3)3·2MeOH- bis[(2-diphenylphosphino)phenyl] ethersilane can reduce electron-deficient olefins selectively and efficiently.
- Zheng, Ai-Jun,Shan, Feng-Jun,Li, Zheng-Ning,Li, Zeng-Chang,Jiang, Lan
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p. 1271 - 1276
(2013/07/19)
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- A facile synthesis of 2h-chromenes and 9-functionalized phenanthrenes through reactions between α,β-unsaturated compounds and arynes
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Facile syntheses of 2H-chromenes or 9-functionalized phenanthrenes under mild conditions in moderate to good yields have been developed. They each involve annulations of arynes with α,β-unsaturated compounds bearing different electron-withdrawing groups (EWGs). Depending on the natures of the different EWGs, the reactions proceed by different pathways: enals react with arynes through a tandem [2+2] cycloaddition/thermal electrocyclic ring-opening/6e-electrocyclization sequence to afford 2H-chromenes, whereas acyl-/ethoxycarbonyl-/cyano-substituted styrenes undergo Diels-Alder reactions with arynes followed by aromatization to afford 9-functionalized phenanthrenes. The scope, limitations, regioselectivities and mechanisms have been studied and are discussed in detail. Depending on the natures of different EWGs in α,β-unsaturated compounds, the reactions between arynes and α,β-unsaturated compounds proceed by different tandem pathways to afford either 2H-chromenes or 9-functionalized phenanthrenes in a selective manner, which is of potential pharmaceutical interest.
- Zhang, Tiexin,Huang, Xian,Wu, Luling
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experimental part
p. 3507 - 3519
(2012/07/30)
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- Iridium-catalyzed α-alkylation of acetonitrile with primary and secondary alcohols
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Acetonitrile is successfully alkylated with primary and secondary alcohols in the presence of t-BuOK using [Ir(OH)- (cod)]2 as a catalyst. This method provides a very clean and atom-economical convenient direct route to substituted nitriles, which are very important raw materials in organic and industrial chemistry.
- Sawaguchi, Takuya,Obora, Yasushi
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supporting information; experimental part
p. 1055 - 1057
(2011/12/05)
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- Monoalkylation of acetonitrile by primary alcohols catalyzed by iridium complexes
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The monoalkylation of acetonitrile by primary alcohols was achieved in a one-pot sequence in the presence of iridium catalysts. A diversity of nitriles has been obtained from aryl- and alkyl-methanols in excellent yield.
- Anxionnat, Bruno,Gomez Pardo, Domingo,Ricci, Gino,Cossy, Janine
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supporting information; experimental part
p. 4084 - 4087
(2011/09/21)
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- Novel system for the synthesis of nitriles from aldehydes using aqueous ammonia and [bis(trifluoroacetoxy)iodo]benzene
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A simple and mild method for the conversion of varieties of aldehydes to the corresponding nitriles using aqueous ammonia and trivalent hypervalent iodine reagent, [bis(trifluoroacetoxy)iodo]benzene, at room temperature is discussed. Advantages of this system are short reaction time, easy workup, and moderate to good yields. Copyright Taylor & Francis Group, LLC.
- Telvekar, Vikas N.,Rane, Rajesh A.,Namjoshi, Tejal V.
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experimental part
p. 494 - 497
(2010/04/04)
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- Hydroxypropyl-a-cyclodextrin-capped palladium nanoparticles: active scaffolds for efficient carbon-carbon bond forming cross-couplings in water
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A new approach for the preparation of palladium nanoparticles in water from a renewable source, 2-hydroxypropyl-a-cyclodextrin (a-HPCD), which acts both as a reductant and capping agent, is presented. The palladium nanoparticles were characterized by using dynamic light scattering (DLS), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS), which revealed the formation of spherical particles in the size range of 2-7 nm. Further analysis by Fourier-transform infrared spectroscopy (FT-IR) and 1H NMR did not show covalent bonds between cyclodextrins and palladium nanoparticles, suggesting that a-HPCD is only physically adsorbed on the nanoparticle surface, presumably through hydrophobic interactions which limit the mutual coalescence of nanoclusters. The catalytic activity was tested in Suzuki, Heck and Sonogashira reactions in neat water, providing good yields and selectivities of coupling products under very low Pd loadings (0.5-0.01 mol%). Remarkably, the nanocatalyst showed significant stability hence the aqueous phase remained active for four subsequent runs. The combination of a binding site for substrates (the HPCD cavity) and a reactive centre (Pd core) provides a potential to explore functional catalysis in aqueous medium.
- Senra, Jaqueline D.,Malta, Luiz Fernando B.,Da Costa, Marcelo E. H. M.,Michel, Ricardo C.,Aguiar, Lucia C. S.,Simas, Alessandro B. C.,Antunes
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supporting information; experimental part
p. 2411 - 2422
(2009/12/28)
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- Palladium on calcium carbonate combined to 2-hydroxypropyl-α/β- cyclodextrins: A selective catalytic system for aqueous heck coupling and hydroarylation
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An efficient, selective and recoverable catalytic system for ligand-free aqueous Heck reactions using hydroxypropylated cyclodextrins (HPCDs) and palladium on calcium carbonate (Pd/CaCO3) is highlighted. Remarkably, stereo- and chemoselectivities could be tuned by the cavity size of cyclodextrins, exploiting the relevance of host-guest interactions. UVVis experiments have led to strong evidence concerning an interplay between Pd(II) and α-HPCD, possibly ascribed to a reduction/stabilization effect of CDs. Unexpectedly, hydroarylation was the favored pathway with acrylonitrile which provided access to 3-phenylpropionitrile derivatives without usual hydride donors. Finally, determination of soluble Pd(0/II) via AAS enabled the definition of a predominant homogeneous mechanism in which TONs over 5000 were observed.
- Senra, Jaqueline D.,Malta, Luiz Fernando B.,Souza, Andrea Luzia F.,Aguiar, Lucia C. S.,Antunesa
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supporting information; experimental part
p. 2551 - 2558
(2009/08/14)
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- A novel system for the synthesis of nitriles from aldehydes using aqueous ammonia and sodium dichloroiodate
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A simple and mild method for the conversion of varieties of aldehydes to the corresponding nitriles using aqueous ammonia and aqueous sodium dichloroiodate reagent at room temperature is discussed. Advantages of this system are short reaction time, easy work-up and moderate to good yields.
- Telvekar, Vikas N.,Patel, Kavit N.,Kundaikar, Harish S.,Chaudhari, Hemchandra K.
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p. 2213 - 2215
(2008/09/18)
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- Novel selective inhibitors of neutral endopeptidase for the treatment of female sexual arousal disorder
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A series of substituted glutaramides were synthesised using Candoxatrilat 1 as a lead and evaluated for potency against neutral endopeptidase (NEP) as a potential treatment for female sexual arousal disorder (FSAD). In this paper, we describe studies in which we were able to increase NEP activity substantially over the levels reported for previous compounds from this programme by appropriate substitution in both the P1′ and P2′ regions. Optimisation led to the 4-chlorophenpropylamide S-30 which was selected as a candidate for further study.
- Pryde, David C.,Cook, Andrew S.,Burring, Denise J.,Jones, Lyn H.,Foll, Stephanie,Platts, Michelle Y.,Sanderson, Vivienne,Corless, Martin,Stobie, Alan,Middleton, Donald S.,Foster, Laura,Barker, Laura,Van Der Graaf, Piet,Stacey, Peter,Kohl, Christopher,Coggon, Sara,Beaumont, Kevin
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p. 142 - 159
(2007/10/03)
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- C-H activation reactions of ruthenium N-heterocyclic carbene complexes: Application in a catalytic tandem reaction involving C-C bond formation from alcohols
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A series of ruthenium hydride N-alkyl heterocyclic carbene complexes has been investigated as catalysts for a tandem oxidation/Wittig/reduction reaction to give C-C bonds from alcohols. The C-H-activated carbene complex Ru(I iPr2Me2)′(PPh3) 2(CO)H (9) proves to be the most active precursor catalyzing the reaction of PhCH2OH and Ph3P=CHCN in 3 h at 70 °C. These results provide (a) a rare case in which N-alkyl carbenes afford higher catalytic activity than their N-aryl counterparts and (b) a novel example of the importance of NHC C-H activation in a catalytic cycle.
- Burling, Suzanne,Paine, Belinda M.,Nama, Devendrababu,Brown, Victoria S.,Mahon, Mary F.,Prior, Timothy J.,Pregosin, Paul S.,Whittlesey, Michael K.,Williams, Jonathan M. J.
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p. 1987 - 1995
(2007/10/03)
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- A novel system for the synthesis of nitriles from carboxylic acids
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A simple, mild and high yielding method for the conversion of various carboxylic acids to nitriles has been developed using diphosphorus tetraiodide in combination with ammonium carbonate at room temperature.
- Telvekar, Vikas N.,Rane, Rajesh A.
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p. 6051 - 6053
(2008/02/10)
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- Direct oxidative conversion of alcohols and amines to nitriles with molecular iodine and DIH in aq NH3
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Simple and high-yield procedures for the direct oxidative conversion of various primary alcohols, and primary, secondary, and tertiary amines to the corresponding nitriles were successfully carried out with molecular iodine in aq ammonia and 1,3-diiodo-5,5-dimethylhydantoin in aq NH3, respectively.
- Iida, Shinpei,Togo, Hideo
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p. 8274 - 8281
(2008/02/08)
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- PROCESS FOR PRODUCTION OF AROMATIC COMPOUNDS
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A problem of the present invention is to provide an economical process with minimized toxicity for producing an aromatic compound having a variety of substituents such as various alkyl groups, and the problem is solved by a process for production of an aromatic compound represented by formula (1) below, which comprises reacting a compound represented by formula (2) below with an aromatic magnesium reagent represented by formula (3a) below in the presence of an iron catalyst and a diamine compound: wherein R is an optionally substituted hydrocarbon group or a C 3 - C 10 saturated or unsaturated ring group; A is an optionally substituted C 4 - C 20 aromatic group or an optionally substituted heteroaromatic group; X is a halogen atom or a sulfonic acid ester; and Y 1 is bromine, iodine, chlorine or a carbanion ligand.
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Page/Page column 27-29
(2010/11/24)
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- Terphenyl-based helical mimetics that disrupt the p53/HDM2 interaction
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(Chemical Equation Presented) HDM2 regulates p53 by binding to its transactivation domain and promoting its ubiquitin-dependent degradation. Crystallographic analysis of the HDM2/p53 complex revealed that three hydrophobic residues (F19, W23, L26) along one face of the p53 helical peptide are essential for binding (see picture). Terphenyl-based antagonists mimic the α-helical region of p53 and disrupt HDM2/p53 complexation.
- Yin, Hang,Lee, Gui-In,Hyung, Soon Park,Payne, Gregory A.,Rodriguez, Johanna M.,Sebti, Said M.,Hamilton, Andrew D.
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p. 2704 - 2707
(2007/10/03)
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- Highly efficient conjugate reduction of α,β-unsaturated nitriles catalyzed by copper/xanthene-type bisphosphine complexes
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α,β-Unsaturated nitriles are chemoselectively reduced to the corresponding saturated nitriles in high yields using a copper-DPEphos or Xantphos complex as catalyst in the presence of polymethylhydrosiloxane (PMHS) as the stoichiometric reducing agent and t-butanol as additive. The Royal Society of Chemistry 2005.
- Kim, Daesung,Park, Bu-Mahn,Yun, Jaesook
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p. 1755 - 1757
(2007/10/03)
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- Direct oxidative conversion of primary alcohols to nitriles using molecular iodine in ammonia water
-
A simple, effective, high-yield procedure for the direct oxidative conversion of alcohols to nitriles, was successfully carried out with molecular iodine in ammonia water. Georg Thieme Verlag Stuttgart.
- Mori, Naoshi,Togo, Hideo
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p. 1456 - 1458
(2007/10/03)
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- Synthesis of Quinolines and 2H-Dihydropyrroles by Nucleophilic Substitution at the Nitrogen Atom of Oxime Derivatives
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Isomerization of oxime derivatives was researched in detail to find out the methods for the syn-anti isomerization of O-substituted oximes. Based on these findings were developed simple methods for the preparation of aza-heterocycles from both stereoisomers of oximes. Quinolines were synthesized from β-aryl ketone oximes by treatment with trifluoroacetic anhydride and 4-chloranil. γ,δ-Unsaturated O-methoxyacetyloximes were transformed to 2H-dihydropyrroles by reaction with methoxy-acetic acid.
- Kitamura, Mitsuru,Yoshida, Masayuki,Kikuchi, Takashi,Narasaka, Koichi
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p. 2415 - 2426
(2007/10/03)
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- Method of using calcilytic compounds
-
The present invention features calcilytic compounds. "Calcilytic compounds" refer to compounds able to inhibit calcium receptor activity. Also described are the use of calcilytic compounds to inhibit calcium receptor activity and/or achieve a beneficial effect in a patient; and techniques which can be used to obtain additional calcilytic compounds.
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- The novel preparation of hydrocinnamonitriles via the reduction of α- phenylsulfonyl cinnamonitriles with SmI2/CH3OH/THF system
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Hydrocinnamonitriles were readily obtained via the reduction of α- phenylsulfonyl cinnamonitriles by SmI2/CH3OH/THF system.
- Guo, Hongyun,Zhang, Yongmin
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p. 1879 - 1885
(2007/10/03)
-
- Structural Effects in the TiO2-Photocatalyzed Oxidation of Alkylaromatic Compounds in Acetonitrile in the Presence of Ag2SO4
-
The TiO2-sensitized photochemical reactions of some alkylbenzenes (ArCH2R; R = H, Me), 1-aryl-2-propanols, and corresponding methyl esters (ArCH2C(OR'')R'CH3; R', R'' = H, Me) have been investigated in MeCN, in the presence of Ag2SO4, which traps the photogenerated electrons.With ArCH2R, the corresponding radical cations are generated by the photoexcited TiO2 and are then deprotonated to from benzyl radicals; from the latter 1,2-diarylethanes, 3-arylpropanonitriles, and benzylacetamides are obtained as major products.With ArCH2C(OR'')R'CH3, the formed radical cations undergo C-C bond cleavage as the only observed route, when Ar = Ph.However, when Ar = 4-MeOPh and R' = H, the radical cation undergoes C-H bond cleavage as the major or exclusive reaction path.These results are compared with those obtained in the corresponding homogeneous photochemical reactions, and their implications with respect to the role of the structure on the side-chain reactivity of aromatic radical cations are discussed.
- Baciocchi, Enrico,Rol, Cesare,Sebastiani, Giovanni V.,Taglieri, Luca
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p. 5272 - 5276
(2007/10/02)
-