103-25-3Relevant articles and documents
Palladium Nanoparticles in Polymers: Catalyst for Alkene Hydrogenation, Carbon-Carbon Cross-Coupling Reactions, and Aerobic Alcohol Oxidation
Park, Cheon Min,Kwon, Min Serk,Park, Jaiwook
, p. 3790 - 3794 (2006)
A new recyclable palladium catalyst was synthesized by a simple procedure from readily available reagents, which is composed of palladium nanoparticles dispersed in an organic polymer. This catalyst is robust, and highly active in many organic transformations including alkene and alkyne hydrogenation, carbon-carbon cross-coupling reactions, and aerobic alcohol oxidation.
Highly regioselective rhodium-catalysed hydroformylation of unsaturated Esters: The first practical method for quaternary selective carbonylation
Clarke, Matthew L.,Roff, Geoffrey J.
, p. 7978 - 7986 (2006)
Highly regioselective hydroformylation of unsaturated esters can be achieved when a highly reactive, ligand-modified, rhodium catalyst is employed near ambient temperatures (15-50°C) and pressures over 30 bar. The use of 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phosphaadamantane shows distinct advantages over other commonly applied phosphanes in terms of reaction rate, and regio- and chemoselectivity. Hydroformylation of a range 1,1-di- and 1,1,2-trisubstituted unsaturated esters yields quaternary aldehydes that are forbidden products according to Keulemans Rule. The aldehydes can be reductively aminated with molecular hydrogen to give β-amino acid esters in high yield. The overall green chemical process involves converting terminal alkynes into unusual β-amino acid esters with only water generated as an essential byproduct. This catalytic system has also been applied to the hydroformylation of simple 1,2-disubstitued unsaturated esters, which have been hydroformylated with excellent α-selectivity and good chemo-selectivity for the first time.
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Noyori et al.
, p. 1542 (1972)
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Acylations and Alkylations of an Ester Enolate in High Yield at Room Temperature on Polystyrene Supports
Chang, Young H.,Ford, Warren T.
, p. 3756 - 3758 (1981)
Polymer-bound esters of 3-phenylpropanoic acid are converted to enolates at room temperature and acylated and alkylated in 73-87percent isolated yields with little or no self-condensation of ester.
Asymmetric hydroesterification of styrene using catalysts with planar-chiral ferrocene oxazoline ligands
Wang, Lailai,Kwok, Wai Him,Chan, Albert S. C.,Tu, Tao,Hou, Xuelong,Dai, Lixin
, p. 2291 - 2295 (2003)
Chiral P,N-ferrocene ligands, 1-diphenylphosphino-1′-[(S)-4-isopropyl-2.5-oxazolinyl]-2′-(S p)-(trimethylsilyl)-ferrocene and its diastereomer, and 1-diphenylphosphino-1′-[(S)-4-isopropyl-2.5-oxazolinyl]-2′(S p)-(diphenylphosphino)-ferrocene and its diastereomer were used in the palladium-catalyzed asymmetric hydroesterification of styrene. The role of these ligands, which contain central, axial, and planar chirality, on the stereochemical outcome was investigated. A significant effect of using CuCl2 as a co-catalyst on the reaction was observed. Excellent regioselectivity (b/n >99:1) with low ee (28%) was obtained in the presence of CuCl2; moderate enantioselectivity (64% ee) but low regioselectivity (b/n, 40/60) was obtained in the absence of CuCl2.
Tris(2,4,6-trimethoxyphenyl)phosphine: Base catalyst in the transformation of α,β-unsaturated aldehydes to saturated carboxylic-acid derivatives
Hayashi, Masahiko,Kawabata, Hirotoshi,Yoshimoto, Kazuya,Tanaka, Takanori
, p. 433 - 445 (2007)
We have focused on the basicity of Tris(2,4,6-trimethoxyphenyl)phosphine (TTMPP) in organic synthesis. To extend the utility of TTMPP, we examined the reaction of α,β-unsaturated aldehydes with trimethylsilyl cyanide in the presence of TTMPP. Furthermore, to clarify the basic character of TTMPP, we measured 31P NMR of TTMPP and related compounds. First, the reaction of cinnamaldehydes with trimethylsilyl cyanide in the presence of a catalytic amount of TTMPP afforded the corresponding saturated carboxylic acids after hydrolysis with 1M HCl. Treatment of the reaction mixture with alcohols or amines instead of 1M HCl gave the corresponding saturated esters and amides, respectively. As a result of studies of the reaction mechanism, it was revealed that the reaction proceeded via silylcyanation of α,β-unsaturated aldehydes with trimethylsilyl cyanide to produce trimethylsilyl ethers of cyanohydrin and subsequent isomerization that formed α-trimethylsiloxy vinyl cyanides, which were hydrolyzed to give saturated carboxylic acids. Copyright Taylor & Francis Group, LLC.
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Yukawa,Tautsumi
, p. 738 (1969)
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Highly efficient and chemoselective transfer hydrogenation of nitroarenes at room temperature over magnetically separable Fe-Ni bimetallic nanoparticles
Petkar, Dhananjay R.,Kadu, Brijesh S.,Chikate, Rajeev C.
, p. 8004 - 8010 (2014)
A highly chemoselective catalytic transfer hydrogenation (CTH) of nitroarenes to corresponding amino derivatives is achieved with Fe-Ni bimetallic nanoparticles (Fe-Ni NP's) as the catalyst and NaBH4 at room temperature. Their catalytic efficiency is ascribed to the presence of Ni sites on the bimetallic surface that not only hinder the surface corrosion of the iron sites but also facilitate efficient electron flow from the catalyst surface to the adsorbed nitro compounds. This facet is corroborated with reusability studies as well as surface characterization of the catalyst before and after its repetitive usage. Thus, these nanoparticles efficiently catalyze the reduction of functionalized nitroarenes to corresponding amines without use of corrosive agents like base or other additives under ambient conditions and are easily separated by a laboratory magnet in an eco-friendly manner.
Microwave-accelerated O-alkylation of carboxylic acids with O-alkylisoureas
Crosignani, Stefano,White, Peter D.,Linclau, Bruno
, p. 2961 - 2963 (2002)
(equation presented) Microwave-assisted O-alkylations of several carboxylic acids have been performed with three different O-alkylisoureas. All reactions are significantly faster compared to conventionally heated reactions, while retaining high chemoselec
Reductive deamination of α-amino carbonyl compounds by means of samarium iodide
Honda, Toshio,Ishikawa, Fumihiro
, p. 1065 - 1066 (1999)
Reaction of α-amino carbonyl compounds with SmI2 in THF-HMPA in the presence of a proton source afforded the deamination products, where the fragmentation occurred between the nitrogen and the carbon α to the carbonyl group.
Hydrogenation of Ketones and Esters Catalyzed by Pd/C?SiO2
Akchurin,Baibulatov,Dokichev
, p. 195 - 198 (2018)
Hydrogenation of unsaturated ketones and esters with molecular hydrogen on the 5%Pd/C?SiO2 heterogeneous catalyst has been studied. The reaction direction and yield are determined by the starting compounds structure. Hydrogenation of unsaturated ketones containing phenyl group at the double carbon–carbon atom is accompanied by the reduction of the ketone group into the alcohol one. Hydrogenation of unsaturated esters is accompanied by transesterification.
Highly efficient solvent-free catalytic hydrogenation of solid alkenes and nitro-aromatics using Pd nanoparticles entrapped in aluminum oxy-hydroxide
Chang, Fei,Kim, Hakwon,Lee, Byeongno,Park, Sungho,Park, Jaiwook
, p. 4250 - 4252 (2010)
Solid alkenes and aromatic nitro compounds are readily hydrogenated to the corresponding alkanes without further reduction of other functional group and amino compounds in nearly quantitative yields in the presence of Pd nanoparticles entrapped in aluminum oxy-hydroxide under the solvent-free condition.
Palladium nanoparticles supported on magnetic carbon-coated cobalt nanobeads: Highly active and recyclable catalysts for alkene hydrogenation
Kainz, Quirin M.,Linhardt, Roland,Grass, Robert N.,Vile, Gianvito,Perez-Ramirez, Javier,Stark, Wendelin J.,Reiser, Oliver
, p. 2020 - 2027 (2014)
Palladium nanoparticles are deposited on the surface of highly magnetic carbon-coated cobalt nanoparticles. In contrast to the established synthesis of Pd nanoparticles via reduction of Pd(II) precursors, the microwave decomposition of a Pd(0) source leads to a more efficient Pd deposition, resulting in a material with considerably higher activity in the hydrogenation of alkenes. Systematic variation of the Pd loading on the carbon-coated cobalt nanoparticle surface reveals a distinct trend to higher activities with decreased loading of Pd. The activity of the catalyst is further improved by the addition of 10 vol% Et2O to iso-propanol that is found to be the solvent of choice. With respect to activity (turnover frequencies up to 11 095 h-1), handling, recyclability through magnetic decantation, and leaching of Pd (≤6 ppm/cycle), this novel magnetic hybrid material compares favorably to conventional Pd/C or Pd@CNT catalysts.
Synthesis and computer-aided analysis of the role of linker for novel ligands of the 5-HT6 serotonin receptor among substituted 1,3,5-triazinylpiperazines
?a?ewska, Dorota,Kurczab, Rafa?,Wi?cek, Ma?gorzata,Sata?a, Grzegorz,Kie?-Kononowicz, Katarzyna,Handzlik, Jadwiga
, p. 319 - 325 (2019)
A series of 2-amino-4-(4-methylpiperazin-1-yl)-1,3,5-triazines was designed based on previously published 2-amino-4-benzyl-(4-methylpiperazin-1-yl)-1,3,5-triazines in order to evaluate the role of a linker between the triazine moiety and an aromatic substituent for the human serotonin 5-HT6 receptor affinity. As new linkers two carbon atoms (ethyl or ethenyl) or an oxyalkyl chain (methoxy, 2-ethoxy, 2-propoxy) were introduced. Affinities of the compounds for the 5-HT6R as the main target, and for the 5-HT1AR, 5-HT7R and D2R as competitive ones, were determined in the radioligand binding assays. Docking to the 5-HT6R homology model was performed to support SAR analysis. Results showed that the branching of the methoxyl linker increased affinity for the human 5-HT6R whereas an unsaturated bond within the linker dramatically reduced desirable activity. Both experimental and theoretical studies confirmed the previously postulated beneficial role of the aromatic size for interaction with the 5-HT6R. Thus, the largest naphthyl moiety yielded the highest activity. In particular, 4-(4-methylpiperazin-1-yl)-6-(1-(naphthalen-1-yloxy)ethyl)-1,3,5-triazin-2-amine (24), the most potent 5-HT6R agent found (Ki = 23 nM), can be a new lead structure for further search and development.
Tandem oxidation of allylic and benzylic alcohols to esters catalyzed by N-heterocyclic carbenes
Maki, Brooks E.,Chan, Audrey,Phillips, Eric M.,Scheidt, Karl A.
, p. 371 - 374 (2007)
(Chemical Equation Presented) N-Heterocyclic carbenes catalyze the oxidation of allylic, propargylic, and benzylic alcohols to esters with manganese(IV) oxide in excellent yields. A variety of ester derivatives can be synthesized, including protected carboxylates. This one-pot tandem oxidation represents the first organocatalytic oxidation of alcohols to esters. Saturated esters can also be accessed from aldehydes using this method. Through the utilization of a chiral catalyst, the acyl-heteroazolium intermediate becomes a chiral acylating agent, which can desymmetrize meso-1,2-diols.
Conversion of α-haloaldehydes into acylating agents by an internal redox reaction catalyzed by nucleophilic carbenes
Reynolds, Nathan T.,De Alaniz, Javier Read,Rovis, Tomislav
, p. 9518 - 9519 (2004)
Reactivity umpolung allows us to consider nontraditional bond disconnections. We report herein that treatment of an α-haloaldehyde with a nucleophile in the presence of catalytic amounts of nucleophilic carbenes results in an internal redox reaction giving rise to a dehalogenated acylating agent as an intermediate by a new reaction manifold. A brief illustration of the scope of this reaction is presented along with evidence supporting the direct intervention of the carbene in the acylation step. Copyright
Pd-catalysed methoxycarbonylation of vinylarenes using chiral monodentate phosphetanes and phospholane as ligands. Effect of substrate substituents on enantioselectivity
Munoz, Bianca K.,Godard, Cyril,Marinetti, Angela,Ruiz, Aurora,Benet-Buchholz, Jordi,Claver, Carmen
, p. 5524 - 5530 (2007)
Palladium complexes bearing phospholane 1 and phosphetane 2-4 ligands have been synthesised to be used as catalyst precursors in the asymmetric methoxycarbonylation of vinyl arenes. Single crystals of the complex [PdCl 2(2)2] II were obtained from a toluene solution and analysed by X-ray crystallography. Using these complexes, excellent regioselectivity (up to 99%) to the branched esters was obtained. Phosphetane ligands provide higher enantioselectivity than the phospholane under the same reaction conditions and an important influence of the substrate was observed. Enantioselectivity up to 50% was obtained using 4-methoxystyrene. The Royal Society of Chemistry.
Aerobic oxidative esterification of primary alcohols over Pd-Au bimetallic catalysts supported on mesoporous silica nanoparticles
Tsai, Chih-Hsiang,Xu, Mengze,Kunal, Pranaw,Trewyn, Brian G.
, p. 81 - 88 (2018)
We have prepared a series of mesoporous silica nanoparticle (MSN) supported Pd-Au bimetallic catalysts using a newly developed sequential impregnation method. These catalysts were fully characterized by various techniques including nitrogen sorption, powder X-ray diffraction, inductively coupled plasma mass spectrometry (ICP-MS), transmission electron microscopy (TEM) and high angle annular dark-field scanning transmission electron microscopy (HADDF-STEM). By using this synthetic approach, we observed metal nanoparticles (NP) with diameters of 1–2 nm homogeneously supported on the MSN. The catalytic performance of these MSN supported metal NPs was tested by aerobic oxidative esterification in a tandem reaction where primary alcohols are oxidized to their corresponding aldehydes and to esters in a subsequent reaction. We determined that Pd NPs are very efficient in the first step of oxidation; however, stagnant in the subsequent oxidation. On the contrary, Au NPs show slow reactivity in converting alcohols to aldehydes, but extraordinarily efficient in the oxidation of aldehydes to esters. By fine tuning the metal ratio, the bimetallic catalyst exhibits better reactivity and selectivity toward a variety of primary alcohols than the corresponding monometallic catalysts. In addition, we also found that the bimetallic Pd-Au@MSN catalysts can be recycled three times without a significant loss in activity.
Platinum nanoparticles supported on ionic liquid-modified magnetic nanoparticles: Selective hydrogenation catalysts
Abu-Reziq, Raed,Wang, Dashan,Post, Michael,Alper, Howard
, p. 2145 - 2150 (2007)
A method for supporting platinum nanoparticles on magnetite nanoparticles is described. The method requires modification of the surface of the magnetic nanoparticles with ionic liquid groups. Before modification, the magnetic nanoparticles are not stable and easily aggregate and, after modification, the magnetite nanoparticles become highly stable and soluble in polar or non-polar organic solvents depending on the alkyl group of the linked ionic liquids. The supporting of platinum nanoparticles on the modified magnetic nanoparticles was achieved by adsorbing platinum salts (K2PtCl4) on the surface of the magnetite nanoparticles via ion exchange with the linked ionic liquid groups and then reducing them by hydrazine. The supported platinum nanoparticles were applied in the catalytic hydrogenation of alkynes in which cis-alkenes were selectively produced, and in the hydrogenation of α,β-unsaturated aldehydes where the allyl alcohols were obtained as the exclusive products. The new catalyst can be easily separated from the reaction mixtures by applying an external magnetic field and recycled.
Palladium-catalyzed reaction of some triphenylbismuth(V) sulfonates and phenolates with methyl acrylate
Gushchin,Malysheva,Kosov,Sharutin
, p. 1249 - 1252 (2006)
Triphenylbismuth(V) derivatives Ph3BiX2 [X = OC 6H2(NO2)3-2,4,6, OC 6H2(NO2-4)Br2-2,6, OTs, OSO 2C6H4OH-4] react with methyl acrylate and PdCl2 (1:3:0.04 molar ratio) in acetonitrile at 20°C to form the cross-coupling products, methyl cinnamate (0.26-0.51 mol mol-1 starting bismuth compound) and methyl hydrocinnamate (0-0.17 mol mol -1); diphenyl, the homocoupling product (0-0.13 mol mol -1); and benzene (0.02-0.15 mol mol-1). The reaction of Ph3Bi(OSO2C6H4OH-4)2 is characterized by the selective formation of methyl cinnamate, but the reagent activity is low. Ph3Bi(OTs)2 exhibits the highest activity among the derivatives studied, but the reaction selectivity is low. The mechanisms of the palladium-catalyzed formation of homo-and cross-coupling products are proposed. Nauka/Interperiodica 2006.
Diversion of the Arbuzov reaction: Alkylation of C-Cl instead of phosphonic ester formation on the fullerene cage
Kraevaya, Ol'Ga A.,Peregudov, Alexander S.,Troyanov, Sergey I.,Godovikov, Ivan,Fedorova, Natalya E.,Klimova, Regina R.,Sergeeva, Vasilina A.,Kameneva, Larisa V.,Ershova, Elizaveta S.,Martynenko, Vyacheslav M.,Claes, Sandra,Kushch, Alla A.,Kostyuk, Svetlana V.,Schols, Dominique,Shestakov, Alexander F.,Troshin, Pavel A.
, p. 7155 - 7160 (2019)
We report an "inversed" Arbuzov reaction of the fullerene derivatives C60Ar5Cl with trialkyl phosphites P(OR)3 producing alkylated fullerene derivatives C60Ar5R (R = Me, Et, iPr, nBu) with almost quantitative yields. This reaction provides a convenient synthetic route for the preparation of a large variety of functionalized fullerene derivatives with tailored properties, e.g. water-soluble compounds demonstrating promising antiviral activities against HCMV, HSV1, HIV and several influenza virus strains.
Hydroesterification of Vinylarenes Catalyzed by Palladium Complexes of Dialkylmonoaryl- and Monoalkyldiarylphosphines
Kawashima, Yasutoyo,Okano, Kentaro,Nozaki, Kyoko,Hiyama, Tamejiro
, p. 347 - 355 (2004)
Hydroesterification of vinylarenes using a mixture of PdCl2 and monodentate phosphorus ligands as a catalyst was studied. As ligands, menthyldiphenylphosphine (MDPP), neomenthyldiphenylphosphine (NMDPP), and dicyclohexyl(phenyl)phosphine (Cy2PPh) were effective to obtain branched esters with high regioselectivity under the moderate reaction conditions without additives such as acids. Not only electronic effects but also steric effects of the cycloalkyl groups were revealed to be significant in order to achieve high catalytic activity. When (S)-2-dicyclopentylphosphino-2′-methoxy-1,1′-binaphthyl was used for the asymmetric hydroesterification of 2-methoxy-6-vinylnaphthalene, (S)-naproxen methyl ester was obtained with 53% ee.
A simple and straightforward approach toward selective C=C bond reduction by hydrazine
Chen, Hao,Wang, Jianmin,Hong, Xuechuan,Zhou, Hai-Bing,Dong, Chune
, p. 758 - 761 (2012)
A simple and straightforward method for reducing the C=C double bond with hydrazine is described. A number of representative C=C bonds in various steric and electronic environments were examined. Substituted alkenes can be selectively reduced in EtOH in the presence of hydrazine to give the corresponding products in up to 100% yields.
Mild and catalytic transesterification reaction using K2HPO 4 for the synthesis of methyl esters
Shinada, Tetsuro,Hamada, Makoto,Miyoshi, Kota,Higashino, Masato,Umezawa, Taiki,Ohfune, Yasufumi
, p. 2141 - 2145 (2010)
K2HPO4 is an efficient catalyst for the transesterification reaction to produce methyl esters. Various functional groups are compatible under the mild reaction conditions. Georg Thieme Verlag Stuttgart New York.
Remarkable effect of bimetallic nanocluster catalysts for aerobic oxidation of alcohols: Combining metals changes the activities and the reaction pathways to aldehydes/carboxylic acids or esters
Kaizuka, Kosuke,Miyamura, Hiroyuki,Kobayashi, Shu
, p. 15096 - 15098 (2010)
Selective oxidation of alcohols catalyzed by novel carbon-stabilized polymer-incarcerated bimetallic nanocluster catalysts using molecular oxygen has been developed. The reactivity and the selectivity were strongly dependent on the combination of metals and solvent systems; aldehydes and ketones were obtained by the gold/platinum catalyst in benzotrifluoride, and esters were formed by the gold/palladium catalyst in methanol. To the best of our knowledge, this is the first example that the reaction pathway has been changed dramatically in gold catalysis by combining with a second metal. The differences in the activity and the selectivity are considered to be derived from the difference in the structure of the bimetallic clusters.
Chemoselective reduction of α,β-unsaturated carbonyl compounds in the presence of CuPd alloy nanoparticles decorated on mesoporous graphitic carbon nitride as highly efficient catalyst
Bayrak, Cetin,Menzek, Abdullah,Sevim, Melike
, (2021/12/09)
Herein, we reported reductions of acid, amide, ester and ketone groups with selectivity (>99%) by the catalytic transfer hydrogenation of with CuPd alloy nanoparticles (NPs) decorated on mesoporous graphitic carbon nitride (Cu50Pd50/mpg-C3N4) catalyst under mild conditions in a water/methanol mixture. CuPd alloy NPs were synthesized by the co-reduction of palladium (II) acetylacetonate and copper(II) acetylacetonate in oleylamine (OAm) solution by the reduction of morpholine-borane solution and then assembled on mpg-C3N4 via liquid phase self‐assembly method. The α, β-unsaturated carbonyl compounds were obtained from the condensation reaction of the benzaldehyde derivatives with acetone derivatives. Cu50Pd50/mpg-C3N4 nanocatalyst was characterized by TEM, XRD, XPS, BET and ICP‐MS. Cu50Pd50/mpg-C3N4 nanocatalyst is highly active catalyst for the reduction of various organic groups and converted to high yield and 99% selectivity. The superior Cu50Pd50/mpg-C3N4 nanocatalyst is highly efficient and reusable catalyst which is reuse after 5 cycle with 98% conversion.
Oxidative esterification of alcohols by a single-side organically decorated Anderson-type chrome-based catalyst
Wang, Jingjing,Jiang, Feng,Tao, Chaofu,Yu, Han,Ruhlmann, Laurent,Wei, Yongge
supporting information, p. 2652 - 2657 (2021/04/21)
The direct esterification of alcohols with non-noble metal-based catalytic systems faces great challenges. Here, we report a new chrome-based catalyst stabilized by a single pentaerythritol decorated Anderson-type polyoxometalate, [N(C4H9)4]3[CrMo6O18(OH)3C{(OCH2)3CH2OH}], which can realize the efficient transformation from alcohols to esters by H2O2oxidation in good yields and high selectivity without extra organic ligands. A variety of alcohols with different functionalities including some natural products and pharmaceutical intermediates are tolerated in this system. The chrome-based catalyst can be recycled several times and still keep the original configuration and catalytic activity. We also propose a reasonable catalytic mechanism and prove the potential for industrial applications.
Direct Deamination of Primary Amines via Isodiazene Intermediates
Berger, Kathleen J.,Driscoll, Julia L.,Yuan, Mingbin,Dherange, Balu D.,Gutierrez, Osvaldo,Levin, Mark D.
supporting information, p. 17366 - 17373 (2021/11/04)
We report here a reaction that selectively deaminates primary amines and anilines under mild conditions and with remarkable functional group tolerance including a range of pharmaceutical compounds, amino acids, amino sugars, and natural products. An anomeric amide reagent is uniquely capable of facilitating the reaction through the intermediacy of an unprecedented monosubstituted isodiazene intermediate. In addition to dramatically simplifying deamination compared to existing protocols, our approach enables strategic applications of iminium and amine-directed chemistries as traceless methods. Mechanistic and computational studies support the intermedicacy of a primary isodiazene which exhibits an unexpected divergence from previously studied secondary isodiazenes, leading to cage-escaping, free radical species that engage in a chain, hydrogen-atom transfer process involving aliphatic and diazenyl radical intermediates.
