- Preparation of a sulfonated carbonaceous material from lignosulfonate and its usefulness as an esterification catalyst
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Sulfonated carbonaceous material useful as a solid acid catalyst was prepared from lignosulfonate, a waste of the paper-making industry sulfite pulping process, and characterized by 13C-NMR, FT-IR, TGA, SEM and elemental analysis, etc. The sulfonic acid group density and total density of all acid groups in the sulfonated carbonaceous material was determined by titration to be 1.24 mmol/g and 5.90 mmol/g, respectively. Its catalytic activity in the esterification of cyclohexanecarboxylic acid with anhydrous ethanol was shown to be comparable to that of the ionic exchange resin Amberlyst-15, when they were used in the same amount. In the meantime, the sulfonic acid group was found to be leached out by 26%-29% after it was exposed to hot water (95 °C) for 5 h. The catalytic usefulness of the prepared carbonaceous material was investigated by performing esterifications.
- Lee, Duckhee
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Read Online
- TEMPERATURE CONTROLLED SELECTIVITY IN METHYLCYCLOPENTANE CARBONYLATION IN HF-SbF5
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Protolytic ionization of methylcyclopentane in HF-SbF5, followed by carbonylation at atmospheric pressure yields either methyl cyclopentane- or cyclohexaneoxocarbenium ions depending on the reaction temperature.An example of kinetic versus thermodynamic control.
- Culmann, Jean-Christophe,Cherry, Ghassan,Jost, Roland,Sommer, Jean
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Read Online
- 4-Alkyl-1,2,4-triazole-3-thione analogues as metallo-β-lactamase inhibitors
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In Gram-negative bacteria, the major mechanism of resistance to β-lactam antibiotics is the production of one or several β-lactamases (BLs), including the highly worrying carbapenemases. Whereas inhibitors of these enzymes were recently marketed, they only target serine-carbapenemases (e.g. KPC-type), and no clinically useful inhibitor is available yet to neutralize the class of metallo-β-lactamases (MBLs). We are developing compounds based on the 1,2,4-triazole-3-thione scaffold, which binds to the di-zinc catalytic site of MBLs in an original fashion, and we previously reported its promising potential to yield broad-spectrum inhibitors. However, up to now only moderate antibiotic potentiation could be observed in microbiological assays and further exploration was needed to improve outer membrane penetration. Here, we synthesized and characterized a series of compounds possessing a diversely functionalized alkyl chain at the 4-position of the heterocycle. We found that the presence of a carboxylic group at the extremity of an alkyl chain yielded potent inhibitors of VIM-type enzymes with Ki values in the μM to sub-μM range, and that this alkyl chain had to be longer or equal to a propyl chain. This result confirmed the importance of a carboxylic function on the 4-substituent of 1,2,4-triazole-3-thione heterocycle. As observed in previous series, active compounds also preferentially contained phenyl, 2-hydroxy-5-methoxyphenyl, naphth-2-yl or m-biphenyl at position 5. However, none efficiently inhibited NDM-1 or IMP-1. Microbiological study on VIM-2-producing E. coli strains and on VIM-1/VIM-4-producing multidrug-resistant K. pneumoniae clinical isolates gave promising results, suggesting that the 1,2,4-triazole-3-thione scaffold worth continuing exploration to further improve penetration. Finally, docking experiments were performed to study the binding mode of alkanoic analogues in the active site of VIM-2.
- Gavara, Laurent,Legru, Alice,Verdirosa, Federica,Sevaille, Laurent,Nauton, Lionel,Corsica, Giuseppina,Mercuri, Paola Sandra,Sannio, Filomena,Feller, Georges,Coulon, Rémi,De Luca, Filomena,Cerboni, Giulia,Tanfoni, Silvia,Chelini, Giulia,Galleni, Moreno,Docquier, Jean-Denis,Hernandez, Jean-Fran?ois
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supporting information
(2021/06/15)
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- Direct Amidation of Esters by Ball Milling**
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The direct mechanochemical amidation of esters by ball milling is described. The operationally simple procedure requires an ester, an amine, and substoichiometric KOtBu and was used to prepare a large and diverse library of 78 amide structures with modest to excellent efficiency. Heteroaromatic and heterocyclic components are specifically shown to be amenable to this mechanochemical protocol. This direct synthesis platform has been applied to the synthesis of active pharmaceutical ingredients (APIs) and agrochemicals as well as the gram-scale synthesis of an active pharmaceutical, all in the absence of a reaction solvent.
- Barreteau, Fabien,Battilocchio, Claudio,Browne, Duncan L.,Godineau, Edouard,Leitch, Jamie A.,Nicholson, William I.,Payne, Riley,Priestley, Ian
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supporting information
p. 21868 - 21874
(2021/09/02)
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- Mild and Selective Rhodium-Catalyzed Transfer Hydrogenation of Functionalized Arenes
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Diboron-mediated rhodium-catalyzed transfer hydrogenation of functionalized arenes is reported. In addition to good functional group tolerance, the reaction features operational simplicity and controllable chemoselectivity. The general applicability of this procedure is demonstrated by the selective hydrogenation of a range of arenes, including functionalized benzenes, biphenyls, and polyaromatics.
- Wang, Yuhan,Chang, Zhiqian,Hu, Yan,Lin, Xiao,Dou, Xiaowei
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supporting information
p. 1910 - 1914
(2021/03/08)
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- Aromatic compound hydrogenation and hydrodeoxygenation method and application thereof
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The invention belongs to the technical field of medicines, and discloses an aromatic compound hydrogenation and hydrodeoxygenation method under mild conditions and application of the method in hydrogenation and hydrodeoxygenation reactions of the aromatic compounds and related mixtures. Specifically, the method comprises the following steps: contacting the aromatic compound or a mixture containing the aromatic compound with a catalyst and hydrogen with proper pressure in a solvent under a proper temperature condition, and reacting the hydrogen, the solvent and the aromatic compound under the action of the catalyst to obtain a corresponding hydrogenation product or/and a hydrodeoxygenation product without an oxygen-containing substituent group. The invention also discloses specific implementation conditions of the method and an aromatic compound structure type applicable to the method. The hydrogenation and hydrodeoxygenation reaction method used in the invention has the advantages of mild reaction conditions, high hydrodeoxygenation efficiency, wide substrate applicability, convenient post-treatment, and good laboratory and industrial application prospects.
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Paragraph 0094-0096; 0098; 0100-0104
(2021/05/29)
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- Ru subnanoparticles on N-doped carbon layer coated SBA-15 as efficient Catalysts for arene hydrogenation
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The N-doped carbon layer coated SBA-15 support has been accomplished via a pyrolysis process. The ultra-low loading Ru nanoparticles (ca. 0.1 wt.%) was incorporated into the support by impregnation and the sequential reduction. The images of HAADF-STEM revealed that the Ru particles with sub-1-nm size (0.2-0.7 nm) were uniformly dispersed on the support. The ultrafine Ru particles displayed the excellent activity for the hydrogenation of olefins, arenes, phenol derivatives and heteroarenes in aqueous phase. The aliphatic or alicyclic compounds were produced selectively without the hydrogenolysis of C–O and C–N bonds. The high turnover frequency (TOF) values can reach up to 10,000 h?1. Notably, the activity of these catalysts improved dramatically with decreasing the sizes of Ru particles. Meanwhile, the N-doped carbon layer coating endowed the high stability of the Ru catalysts and prevented the leaching of the Ru species owning to the strong interaction between doped-N atoms and the ultrafine Ru particles. Overall, this work provides a highly attractive strategy to construct the supported sub-1-nm Ru particles utilized for the aqueous hydrogenation.
- Qian, Wei,Lin, Lina,Qiao, Yunxiang,Zhao,Xu, Zichen,Gong, Honghui,Li,Chen,Huang, Rong,Hou, Zhenshan
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- Recyclable Rh-PVP nanoparticles catalyzed hydrogenation of benzoic acid derivatives and quinolines under solvent-free conditions
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Various transition metal nanoparticles, prepared by microwave-assisted alcohol reduction method were examined for hydrogenation of benzoic acid to cyclohexanecarboxylic acid under solvent-free conditions. Rh metal was the most effective catalyst over other metal catalyst. The catalyst showed moderate to high yield for the hydrogenation of substituted benzoic acid and substituted quinolines. Rh-PVP was recycled four times with a minor loss in catalytic activity.
- Chaudhari, Chandan,Imatome, Hirotaka,Nishida, Yoshihide,Sato, Katsutoshi,Nagaoka, Katsutoshi
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- Chemoselective Hydrogenation of α,β-Unsaturated Carbonyls Catalyzed by Biomass-Derived Cobalt Nanoparticles in Water
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Herein, we report highly chemoselective hydrogenation of α,β-unsaturated carbonyls to saturated carbonyls catalyzed by cobalt nanoparticles supported on the biomass-derived carbon from bamboo shoots with molecular hydrogen in water, which is the first prototype using a heterogeneous non-noble metal catalyst for such organic transformation as far as we know. The optimal cobalt nanocatalyst, CoOx@NC-800, manifested remarkable activity and selectivity for hydrogenation of C=C in α,β-unsaturated carbonyls under mild conditions. A broad set of α,β-aromatic and aliphatic unsaturated carbonyls were selectively reduced to their corresponding saturated carbonyls in up to 99 % yields with good tolerance of various functional groups. Meanwhile, a new straightforward one-pot cascade synthesis of saturated carbonyls was realized with high activity and selectivity via the cross-aldol condensation of ketones with aldehydes followed by selective hydrogenation. More importantly, this one-pot strategy is applicable for the expedient synthesis of Loureirin A, a versatile bioactive and medicinal molecule, from readily available starting materials, further highlighting the practical utility of the catalyst. In addition, the catalyst can be easily separated for successive reuses without significant loss in both activity and selectivity.
- Song, Tao,Ma, Zhiming,Yang, Yong
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p. 1313 - 1319
(2019/01/25)
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- Hydrogenation of (Hetero)aryl Boronate Esters with a Cyclic (Alkyl)(amino)carbene–Rhodium Complex: Direct Access to cis-Substituted Borylated Cycloalkanes and Saturated Heterocycles
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We herein report the hydrogenation of substituted aryl- and heteroaryl boronate esters for the selective synthesis of cis-substituted borylated cycloalkanes and saturated heterocycles. A cyclic (alkyl)(amino)carbene-ligated rhodium complex with two dimethyl groups at the ortho-alkyl scaffold of the carbene showed high reactivity in promoting the hydrogenation, thereby enabling the hydrogenation of (hetero)arenes with retention of the synthetically valuable boronate group. This process constitutes a clean, atom-economic, as well as chemo- and stereoselective route for the generation of cis-configured, diversely substituted borylated cycloalkanes and saturated heterocycles that are usually elusive and difficult to prepare.
- Ling, Liang,He, Yuan,Zhang, Xue,Luo, Meiming,Zeng, Xiaoming
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supporting information
p. 6554 - 6558
(2019/04/17)
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- ORGANIC COMPOUNDS
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Disclosed are fragrance compositions comprising ethyl cyclohexanoate.
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Page/Page column 7-8
(2018/12/13)
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- SPIRO-LACTAM NMDA RECEPTOR MODULATORS AND USES THEREOF
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Disclosed are compounds having potency in the modulation of NMDA receptor activity. Such compounds can be used in the treatment of conditions such as depression and related disorders. Orally delivered formulations and other pharmaceutically acceptable delivery forms of the compounds, including intravenous formulations, are also disclosed.
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Page/Page column 43-44
(2018/03/09)
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- Polysilane-Immobilized Rh-Pt Bimetallic Nanoparticles as Powerful Arene Hydrogenation Catalysts: Synthesis, Reactions under Batch and Flow Conditions and Reaction Mechanism
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Hydrogenation of arenes is an important reaction not only for hydrogen storage and transport but also for the synthesis of functional molecules such as pharmaceuticals and biologically active compounds. Here, we describe the development of heterogeneous Rh-Pt bimetallic nanoparticle catalysts for the hydrogenation of arenes with inexpensive polysilane as support. The catalysts could be used in both batch and continuous-flow systems with high performance under mild conditions and showed wide substrate generality. In the continuous-flow system, the product could be obtained by simply passing the substrate and 1 atm H2 through a column packed with the catalyst. Remarkably, much higher catalytic performance was observed in the flow system than in the batch system, and extremely strong durability under continuous-flow conditions was demonstrated (>50 days continuous run; turnover number >3.4 × 105). Furthermore, details of the reaction mechanisms and the origin of different kinetics in batch and flow were studied, and the obtained knowledge was applied to develop completely selective arene hydrogenation of compounds containing two aromatic rings toward the synthesis of an active pharmaceutical ingredient.
- Miyamura, Hiroyuki,Suzuki, Aya,Yasukawa, Tomohiro,Kobayashi, Shu
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supporting information
p. 11325 - 11334
(2018/09/06)
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- Alkoxycarbonylation of olefins with carbon dioxide by a reusable heterobimetallic ruthenium-cobalt catalytic system
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The heterobimetallic ruthenium-cobalt catalytic system exhibited good catalytic performance and reusability in the reductive alkoxycarbonylation of olefins with carbon dioxide. Compared to the previous system only consisting of ruthenium catalyst, the binary catalyst system effectively reduced the usage of noble metal and ionic liquid additives. The respective contribution of ruthenium and cobalt catalysts in this multiple-step catalytic process was investigated by a series of condition-controlled experiments. The evolution of the ruthenium catalyst and the occurrence of alkene hydrogenation during the reaction was explained by theortical calculations.
- Zhang, Xuehua,Shen, Chaoren,Xia, Chungu,Tian, Xinxin,He, Lin
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supporting information
p. 5533 - 5539
(2019/01/03)
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- Direct C-C Bond Formation from Alkanes Using Ni-Photoredox Catalysis
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A method for direct cross coupling between unactivated C(sp3)-H bonds and chloroformates has been accomplished via nickel and photoredox catalysis. A diverse range of feedstock chemicals, such as (a)cyclic alkanes and toluenes, along with late-stage intermediates, undergo intermolecular C-C bond formation to afford esters under mild conditions using only 3 equiv of the C-H partner. Site selectivity is predictable according to bond strength and polarity trends that are consistent with the intermediacy of a chlorine radical as the hydrogen atom-abstracting species.
- Ackerman, Laura K. G.,Martinez Alvarado, Jesus I.,Doyle, Abigail G.
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supporting information
p. 14059 - 14063
(2018/10/24)
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- One-pot dichlorinative deamidation of primary β-ketoamides
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An approach to the dichlorinative deamidation of primary β-ketoamides through ketonic cleavage is described, and a series of α,α-dichloroketones were furnished mostly in the presence of TEMPO. Based on control experiments, a mechanism involving tandem dichlorination and deamidation is proposed to interpret the observed reactivity.
- Zheng, Congke,Zhang, Xiaohui,Ijaz Hussain, Muhammad,Huang, Mingming,Liu, Qing,Xiong, Yan,Zhu, Xiangming
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supporting information
p. 574 - 577
(2017/01/16)
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- Upgrading of aromatic compounds in bio-oil over ultrathin graphene encapsulated Ru nanoparticles
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Fast pyrolysis of biomass for bio-oil production is a direct route to renewable liquid fuels, but raw bio-oil must be upgraded in order to remove easily polymerized compounds (such as phenols and furfurals). Herein, a synthesis strategy for graphene encapsulated Ru nanoparticles (NPs) on carbon sheets (denoted as Ru@G-CS) and their excellent performance for the upgrading of raw bio-oil were reported. Ru@G-CS composites were prepared via the direct pyrolysis of mixed glucose, melamine and RuCl3 at varied temperatures (500-800 °C). Characterization indicated that very fine Ru NPs (2.5 ± 1.0 nm) that were encapsulated within 1-2 layered N-doped graphene were fabricated on N-doped carbon sheets (CS) in Ru@G-CS-700 (pyrolysis at 700 °C). And the Ru@G-CS-700 composite was highly active and stable for hydrogenation of unstable components in bio-oil (31 samples including phenols, furfurals and aromatics) even in aqueous media under mild conditions. This work provides a new protocol to the utilization of biomass, especially for the upgrading of bio-oil.
- Shi, Juanjuan,Zhao, Mengsi,Wang, Yingyu,Fu, Jie,Lu, Xiuyang,Hou, Zhaoyin
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supporting information
p. 5842 - 5848
(2016/05/24)
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- Oxidative Alkane C?H Alkoxycarbonylation
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Directly utilizing a chemical feedstock to construct valuable compounds is an attractive prospect in organic synthesis. In particular, the combination of C(sp3)?H activation and oxidative carbonylation involving alkanes and CO gas is a promising and efficient method to synthesize carbonyl derivatives. However, due to the high C?H bond dissociation energy and low polarity of unactivated alkanes, the carbonylation of unactivated C(sp3)?H bonds still remains a great challenge. In this work, we introduce a palladium-catalyzed radical oxidative alkoxycarbonylation of alkanes to prepare numerous alkyl carboxylates. Various alkanes and alcohols were compatible, generating the desired products in up to 94 % yield. Remarkably, ethane, a constituent of natural gas, could be employed as a substrate under the standard reaction conditions. Preliminary mechanistic studies revealed a probable palladium-catalyzed radical process.
- Lu, Lijun,Shi, Renyi,Liu, Luyao,Yan, Jingwen,Lu, Fangling,Lei, Aiwen
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supporting information
p. 14484 - 14488
(2016/10/03)
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- Cycloalkyl carboxylic acid ester compound preparation method
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The present invention discloses a cycloalkyl formate compound preparation method, wherein in the presence of a palladium salt and a peroxide, a cycloalkane compound and an alcohol compound are dissolved in an organic solvent, the system is replaced by a carbon monoxide atmosphere, a reaction is performed for 16-24 h at a reaction temperature of 90-120 DEG C, and separation and purification are performed to obtain the cycloalkyl formate compound. According to the present invention, the used reactants are cheap and easy to obtain, the reaction conditions are simple, the atom economy is high, and the high-selectivity oxidation carbonylation reaction of the cycloalkane compound and the alcohol compound can be achieved so as to obtain the cycloalkyl formate compound; with the method, the precursor of the widely-used drug dicyclomine having treatment effects on intestines and stomach cramps and irritable bowel syndrome can be simply prepared; and the method has application potential in synthesis of drugs, natural products and the like.
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Paragraph 0027; 0028; 0053
(2019/02/04)
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- A Lamellar Coordination Polymer with Remarkable Catalytic Activity
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A positively charged lamellar coordination polymer based on a flexible triphosphonic acid linker is reported. [Gd(H4nmp)(H2O)2]Cl?2 H2O (1) [H6nmp=nitrilotris(methylenephosphonic acid)] was obtained by a one-pot approach by using water as a green solvent and by forcing the inclusion of additional acid sites by employing HCl in the synthesis. Compound 1 acts as a versatile heterogeneous acid catalyst with outstanding activity in organic reactions such as alcoholysis of styrene oxide, acetalization of benzaldehyde and cyclohexanaldehyde and ketalization of cyclohexanone. For all reaction systems, very high conversions were reached (92–97 %) in only 15–30 min under mild conditions (35 °C, atmospheric pressure). The coordination polymer exhibits a protonic conductivity of 1.23×10?5S cm?1at 98 % relative humidity and 40 °C.
- Mendes, Ricardo F.,Antunes, Margarida M.,Silva, Patrícia,Barbosa, Paula,Figueiredo, Filipe,Linden, Anthony,Rocha, Jo?o,Valente, Anabela A.,Almeida Paz, Filipe A.
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p. 13136 - 13146
(2016/09/09)
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- Method for manufacture of a solid acid catalyst of sulfonated carbon using sulfonated lignin and for preparation of organic compounds using the catalyst made with the same method
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The present invention refers to lignosulfonate method and manufacturing method using solid acid opinion phone carbon and preparation manufacturing method of organic compounds using opinion phone carbon is provided to formula (1) a device (lignosulfonate) [...] rig of or molecular and a polyhydric alcohol main of carbon in two or more cations provided of materials that can for controlling strip tension of reactants sulfate (H 2 SO 4), an engineered oelum, trioxide (SO 3) and nick opinion gun it buys (chlorosulfonic acid, HSO 3 Cl) presence of one of the more absorbents selected from comprising the step of reacting under to formula (2) of preparing opinion phone carbon characterized by lignosulfonate method and manufacturing method using solid acid opinion phone carbon and preparation manufacturing method of organic compounds using opinion phone carbon relates to. ... Formula (1) ... Formula (2) Said formula (1) and formula (2) in the H M, Li, Na, one more absorbents selected from K, Na or H is preferably, more preferably is H. (by machine translation)
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Paragraph 0127; 0128
(2016/12/16)
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- Synthesis of 3-hydroxyindanones via potassium salt of amino acid catalyzed regioselective intramolecular aldolization of ortho-diacylbenzenes
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First organocatalytic intramolecular aldolization of ortho-diacylbenzenes to construct highly functionalized 3-hydroxyindanones is described. In this transformation a high trans-selectivity is achieved by the use of metal salt of amino acid. This method allows an easy access to the strained spirocyclic 3-hydroxyindanones related to a number of natural product frameworks. Synthesis of a new class of indole skeleton substituted by 3-hydroxyindanones added an extra essence to this new protocol.
- Chanda, Tanmoy,Chowdhury, Sushobhan,Anand, Namrata,Koley, Suvajit,Gupta, Ashutosh,Singh, Maya Shankar
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supporting information
p. 981 - 985
(2015/03/04)
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- Facile arene hydrogenation under flow conditions catalyzed by rhodium or ruthenium on carbon
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An efficient and practical protocol for the flow hydrogenation of aromatic rings was developed. The hydrogenation of a variety of aromatic compounds, such as benzene, furan, and pyridine derivatives, could be completed within only 20 s during a single pass through a catalyst cartridge containing 10 % rhodium on carbon (Rh/C) or 10 % ruthenium on carbon (Ru/C) under neutral conditions. The protocol was successfully applied to a 10 mmol scale reaction. Furthermore, the 10 % Rh/C and 10 % Ru/C did not deteriorate during the entire study.
- Hattori, Tomohiro,Ida, Takashi,Tsubone, Aya,Sawama, Yoshinari,Monguchi, Yasunari,Sajiki, Hironao
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supporting information
p. 2492 - 2497
(2015/04/22)
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- Transition metal nanoparticles stabilized by ammonium salts of hyperbranched polystyrene: effect of metals on catalysis of the biphasic hydrogenation of alkenes and arenes
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Abstract Hyperbranched polystyrene bearing ammonium salts (HPS-NR3+Cl-) behaves as an excellent stabilizer of ruthenium, rhodium, iridium, palladium, and platinum nanoparticles from 1 to 3 nm in size uniformly dispersed in the polymer matrix. The catalytic performance of the resulting metal-polymer composites, M@HPS-NR3+Cl-, is dependent on the metal. This dependence was investigated by assessing the hydrogenation of alkenes and arenes. The utility of M@HPS-NR3+Cl- as reusable catalysts in aqueous/organic biphasic systems was demonstrated by examining the catalysis of the hydrogenation of aromatic compounds containing various functional groups by Ru@HPS-NR3+Cl-.
- Gao, Lei,Kojima, Keisuke,Nagashima, Hideo
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p. 6414 - 6423
(2015/08/18)
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- An efficient one-pot oxidative esterification of aldehydes to carboxylic esters using B(C6F5)3-TBHP
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A simple and efficient protocol for oxidative esterification of diverse aldehydes with alcohols was accomplished with tert-butyl hydroperoxide and 1 mol % of tris(pentafluorophenyl)borane [B(C6F5)3] to generate the corresponding esters in good to excellent yields. The present protocol represents compatibility with wide range of functional groups as well as exceptional tolerance toward acid labile protecting groups such as TBDPS, TBDMS, acetonide, and Boc.
- Guggilapu, Sravanthi Devi,Prajapti, Santosh Kumar,Babu, Bathini Nagendra
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supporting information
p. 889 - 892
(2015/02/05)
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- A NiPdB-PEG(800) amorphous alloy catalyst for the chemoselective hydrogenation of electron-deficient aromatic substrates
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A new Pd and polyethylene glycol 800 [PEG(800)]-modified NiB [NiPdB-PEG(800)] amorphous alloy catalyst was prepared, which demonstrated excellent activities, similar to those of noble metal catalysts, in the chemoselective hydrogenation of a series of electron-deficient aromatic substrates in water. The addition of small amounts of Pd to NiB markedly improved its activity. The Pd not only benefits the dispersion of active species but also contributes to the activity of the catalyst. The accompanying agglomeration can be inhibited with the further addition of PEG(800), which results in the largest surface area, the smallest particle size, and the greatest number of active species, resulting in optimum H2- chemisorption and accounting for its highest activity. The key factors determining the main reaction products depend not only on the structures of the substrates but also on the character of the solvents. Water is found to be the most effective solvent for most of the substrates. Disperse and be active! A Pd and polyethylene glycol 800 [PEG(800)]-modified NiB [NiPdB-PEG(800)] amorphous alloy catalyst demonstrates excellent activities, similar to those of noble metal catalysts, in the chemoselective hydrogenation of a series of electron-deficient aromatic substrates in water. The addition of Pd benefits the dispersion of active species and contributes to the activity of the catalyst. Copyright
- Bai, Guoyi,Zhao, Zhen,Dong, Huixian,Niu, Libo,Wang, Yalong,Chen, Qingzhi
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p. 655 - 662
(2014/03/21)
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- Post-functionalized iridium-Zr-MOF as a promising recyclable catalyst for the hydrogenation of aromatics
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The multifunctional heterogeneous catalyst iridium-Zr-based MOF is able to effectively catalyze the hydrogenation of aromatic compounds in high yields under mild conditions. The catalyst was found to be highly active and reusable, giving similar reactivity and selectivity after at least five catalytic uses. This journal is the Partner Organisations 2014.
- Rasero-Almansa, Antonia M.,Corma, Avelino,Iglesias, Marta,Sanchez, Felix
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p. 3522 - 3527
(2014/07/08)
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- Magnesium-catalyzed hydroboration of esters: Evidence for a new zwitterionic mechanism
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A magnesium-catalyzed ester hydroboration reaction rapidly and efficiently (a pathway involving a zwitterionic alkoxyborate is proposed. The Royal Society of Chemistry 2014.
- Mukherjee, Debabrata,Ellern, Arkady,Sadow, Aaron D.
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p. 959 - 964
(2014/03/21)
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- Palladium complexes with N-heterocyclic carbene ligands as catalysts for the alkoxycarbonylation of olefins
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Palladium catalysts, generated from Pd(OAc)2 and 2 equiv of N,N-dialkylbenzimidazolium iodide, are effective for the alkoxycarbonylation of olefins in high yields (>90%). Alkoxycarbonylation of 1-hexene in dimethylacetamide is achieved within 24 h at 110 C using 1 mol % catalyst, 1000 psi CO, and ethanol. Reactions can be prepared in air, without the need of an acid additive to produce ethyl 2-methylhexanoate and ethyl heptanoate in approximately a 2:1 ratio.
- Roberts, Gina M.,Pierce, Philip J.,Woo, L. Keith
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p. 2033 - 2036
(2013/05/21)
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- NOVEL CARBOXAMIDE DERIVATIVES AS HIV INHIBITORS
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The present invention relates to carboxamide derivatives of Formula (I), where B1, B2, X, L, n, R, R1, R2, Z1, Z2, Rx and Ry are as defined in the claims, as compounds and compositions for inhibiting Human Immunodeficiency Virus (HIV) and process for making the compounds.
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Page/Page column 26-27
(2011/06/19)
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- Rh(0) colloids supported on TiO2: A highly active and pertinent tandem in neat water for the hydrogenation of aromatics
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TiO2-supported Rh(0) nanoparticles were easily prepared in one step without calcination by a room temperature impregnation of the inorganic support with a prestabilized colloidal Rh(0) suspension. They are highly active and reusable catalysts for the hydrogenation of aromatics and chloroanisole derivatives in neat water with TOFs up to 33000 h-1. The comparison with the analogous silica system Rh@SiO2 was discussed showing higher catalytic selectivities and activities with Rh(0) colloids supported on TiO2.
- Hubert, Claudie,Bile, Elodie Guyonnet,Denicourt-Nowicki, Audrey,Roucoux, Alain
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experimental part
p. 1766 - 1771
(2011/09/19)
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- NOVEL PROCESS
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The present invention relates to a process for the preparation of 1-(2-ethyl-butyl)-cyclohexanecarboxylic acid which is useful as an intermediate in the preparation of pharmaceutically active compounds.
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Page/Page column 4
(2009/12/27)
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- Rhodium nanoparticles supported on carbon nanofibers as an arene hydrogenation catalyst highly tolerant to a coexisting epoxido group
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Rhodium nanoparticles supported on a carbon nanofiber (Rh/CNF-T) show high catalytic activity toward arene hydrogenation under mild conditions in high turnover numbers without leaching the Rh species; the reaction is highly tolerant to epoxido groups, which often undergo ring-opening hydrogenation with conventional catalysts.
- Motoyama, Yukihiro,Takasaki, Mikihiro,Yoon, Seong-Ho,Mochida, Isao,Nagashima, Hideo
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supporting information; experimental part
p. 5042 - 5045
(2009/12/28)
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- Polyhydroxylated ammonium chloride salt: A new efficient surfactant for nanoparticles stabilisation in aqueous media. Characterization and application in catalysis
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A trihydroxyammonium chloride has proved to be an efficient protective agent for Rh(0) nanoparticles and the hydrogenation of arene compounds has been investigated. Significant formation of cyclohexanone in the reduction of anisole has been demonstrated. The Royal Society of Chemistry 2009.
- Hubert, Claudie,Denicourt-Nowicki, Audrey,Guegan, Jean-Paul,Roucoux, Alain
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experimental part
p. 7356 - 7358
(2010/01/06)
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- Palladium(II) carboxylates and palladium(I) carbonyl carboxylate complexes as catalysts for olefin cyclopropanation with ethyl diazoacetate
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Palladium(I) carbonyl carboxylate complexes [Pd(μ-CO)(μ-RCO 2)]n (R = Me, n = 4; R = CMe3, n = 6) and the corresponding palladium(II) carboxylates (acetate and pivalate) catalyze the cyclopropanation of olefins with ethyl diazoacetate. The performance of these catalysts is similar in terms of selectivity and cyclopropane yields, regardless of the oxidation state of the metal center. However the rates of the cyclopropanation reactions are significantly higher for the acetate based catalysts than for the pivalate derivatives, which suggests that the main catalytic species are carboxylate containing palladium complexes. Kinetic measurements show that reaction rates are independent of the olefin concentration when these are 1-hexene or styrene, but norbornene exerts an inhibitory effect. In spite of this, competition experiments indicate that the cyclopropanation of styrene is 2.2 times as favorable as that of 1-hexene for any of the four catalysts. These observations indicate that while the rate-determining formation of the intermediate palladium carbenoid species is controlled by the catalyst structure, this is followed by a rapid and less specific cyclopropanation step that is not affected by the nature of the carboxylate groups present in the catalyst. An independent test using a 1:1 benzene/cyclohexane mixture of solvents showed that the transfer of ethoxycarbonylcarbene (:C(CO2Et)H) to these molecules is unselective (relative rate of benzene/cyclohexane functionalization ≈1.8, independent of the catalyst). This result can be interpreted as an indication of the involvement of free ethoxycarbonylcarbene in the carbene transfer step. The Royal Society of Chemistry 2009.
- Shishilov, Oleg N.,Stromnova, Tatiana A.,Campora, Juan,Palma, Pilar,Cartes, M. Angeles,Martinez-Prieto, Luis Miguel
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experimental part
p. 6626 - 6633
(2010/02/16)
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- Magnesium nitride as a convenient source of ammonia: Preparation of primary amides
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(Chemical Equation Presented) The use of magnesium nitride (Mg 3N2) as a convenient source of ammonia has been explored for the direct transformation of esters to primary amides. Methyl, ethyl, isopropyl, and tert-butyl esters are converted to the corresponding carboxamides in good yields (75-99%).
- Veitch, Gemma E.,Bridgwood, Katy L.,Ley, Steven V.
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scheme or table
p. 3623 - 3625
(2009/05/07)
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- Methylated cyclodextrins: An efficient protective agent in water for zerovalent ruthenium nanoparticles and a supramolecular shuttle in alkene and arene hydrogenation reactions
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Zerovalent ruthenium(0) nanoparticles in the size range of 2.5 nm were easily prepared by chemical reduction of ruthenium salt with an excess amount of sodium borohydride and were efficiently stabilized by methylated cyclodextrins. The optimization of the catalytic system has been carried out in terms of stability and catalytic activity, considering the hydrogenation of olefinic compounds under biphasic liquid-liquid conditions. Efficient and controlled chemoselectivities were obtained in the hydrogenation of arene derivatives by the relevant choice of cavity and methylation degree of the cyclodextrins. Finally, the hydrogenation of α- and β-pinenes leads to the major formation of cis-pinanes, interesting synthons for fine chemistry, with high diastereoisomeric excesses. This journal is The Royal Society of Chemistry.
- Denicourt-Nowicki, Audrey,Ponchel, Anne,Monflier, Eric,Roucoux, Alain
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p. 5714 - 5719
(2008/09/17)
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- Rhodium and iridium nanoparticles entrapped in aluminum oxyhydroxide nanofibers: Catalysts for hydrogenations of arenes and ketones at room temperature with hydrogen balloon
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The recyclable metal nanoparticle catalysts, rhodium in aluminum oxyhydroxide [Rh/ AlO(OH)] and iridium in aluminum oxyhydroxide [Ir/A1O(OH)], were simply prepared from readily available reagents. The catalysts showed high activities in the hydrogenation of various arenes and ketones under mild conditions. Selective hydrogenation was possible for bicyclic and tricyclic arenes in high yields. The catalysts were active at room temperature even with a hydrogen balloon. Also, the catalysts showed high turnover frequency (TOF) values under solventless conditions at 75 °C under 4 atm hydrogen pressure: ca. 1700h 1 in the hydrogenation of benzene. Furthermore, Rh/A1O(OH) can be reused forat least 10 times without activity loss. The catalysts were characterized by the transmission electron microscopy (TEM), powder X-ray diffraction (XRD), inductively coupled plasma (ICP), energy dispersive X-ray analysis (EDX), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption and hydrogen chemisorption experiments. The sizes of rhodium and iridium particles were estimated to be 3-4 nm and 2-3 nm, respectively. Aluminum oxyhydroxide nanofibers of these catalysts have surface areas of 500-600 m2 g -1.
- Park, In Soo,Kwon, Min Serk,Kang, Kyung Yeon,Lee, Jae Sung,Park, Jaiwook
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p. 2039 - 2047
(2008/09/17)
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- Nanoheterogeneous catalytic hydrogenation of arenes: Evaluation of the surfactant-stabilized aqueous ruthenium(O) colloidal suspension
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The hydrogenation of various aromatic compounds by a surfactant-stabilized aqueous ruthenium(O) colloidal suspension was investigated. The nanocatalysts in the size range of 2.5-3.5 nm were synthesized by reducing ruthenium trichloride salt with sodium borohydride and were stabilized by the highly water soluble N,N-dimethyl-N-cetyl-N-(2-hydroxyethyl)ammonium chloride salt according to our classical approach. The efficient catalytic reactions were performed at room temperature and under hydrogen pressure. The effect of the stirring, namely magnetic stir bar or gas projection impeller, was also studied. A comparison with an analogous rhodium nanocatalyst is described.
- Nowicki, Audrey,Boulaire, Virginie Le,Roucoux, Alain
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p. 2326 - 2330
(2008/09/18)
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- A new versatile synthesis of esters from Grignard reagents and chloroformates
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Cross-coupling reactions of chloroformates with organocopper reagents, derived from Grignard reagents, cuprous bromide and lithium bromide, provide a rapid and straightforward method for the synthesis of esters. Georg Thieme Verlag Stuttgart.
- Bottalico, Daniela,Fiandanese, Vito,Marchese, Giuseppe,Punzi, Angela
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p. 974 - 976
(2008/02/02)
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- A simple and reproducible method for the synthesis of silica-supported rhodium nanoparticles and their investigation in the hydrogenation of aromatic compounds
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Colloidal suspensions of rhodium nanoparticles have been easily prepared in aqueous solution by chemical reduction of the precursor RhCl 3·3H2O in the presence of the surfactant N,N-dimethyl-N-cetyl-N-(2-hydroxyethyl)ammonium chloride (HEA16Cl) and further used to immobilize rhodium nanoparticles on silica by simple impregnation. The obtained silica-supported rhodium nanoparticles have been investigated by adapted characterization methods such as transmission electron microscopy and X-ray photoelectron spectroscopy. A particle size increase from 2.4 to 5 nm after the silica immobilization step and total elimination of the surfactant has been observed. This "heterogeneous" catalyst displayed good activities for the hydrogenation of mono-, di- alkylsubstituted and/or functionalized aromatic derivatives in water under atmospheric hydrogen pressure and at room temperature. In all cases, the catalyst could be recovered several times after a simple decantation or filtration and reused without any significant loss in catalytic activity. This supported catalyst has also been tested under higher hydrogen pressure giving rise to TOFs reaching 6430 h -1 at 30 bar and in terms of catalytic lifetime 30 000 TTO in 8.5 h for pure anisole hydrogenation at 40 bar. the Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2006.
- Mevellec, Vincent,Nowicki, Audrey,Roucoux, Alain,Dujardin, Christophe,Granger, Pascal,Payen, Edmond,Philippot, Karine
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p. 1214 - 1219
(2007/10/03)
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- Highly-dispersed and size-controlled ruthenium nanoparticles on carbon nanofibers: Preparation, characterization, and catalysis
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Facile synthesis of ruthenium nanoparticles supported on the carbon nanofibers (CNFs) is accomplished by thermal decomposition of Ru 3(CO)12; ruthenium species on the platelet-type CNF are dispersed homogeneously and selectively on the edge of the graphite layers with narrow size distributions and behaves as an excellent catalyst for arene hydrogenation. Copyright
- Motoyama, Yukihiro,Takasaki, Mikihiro,Higashi, Kenji,Yoon, Seong-Ho,Mochida, Isao,Nagashima, Hideo
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p. 876 - 877
(2007/10/03)
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- Efficient esterification of carboxylic acids and phosphonic acids with trialkyl orthoacetate in ionic liquid
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An operationally simple, inexpensive, efficient, and environmentally friendly esterification of various carboxylic acids, phosphonic acids, and phosphinic acids with triethyl orthoacetate or trimethyl orthoacetate under neutral conditions in a typical room temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate, was successfully carried out to provide the corresponding ethyl esters or methyl esters in high yields.
- Yoshino, Tomonori,Imori, Satomi,Togo, Hideo
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p. 1309 - 1317
(2007/10/03)
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- Facile preparation of polymer-supported methyl sulfonate and its recyclable use for methylation of carboxylic acids and amines
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A simple and efficient one-pot procedure for the preparation of polymer-supported methyl sulfonate from the reaction of polymer-supported sulfonic acid with trimethyl orthoacetate was achieved, and it could be successfully used for efficient methylation of carboxylic acids, phosphonic acids, sulfinic acids, amines, thiol, and phenol. Moreover, the polymer reagent could be recovered, regenerated, and reused easily for the same reactions. Georg Thieme Verlag Stuttgart.
- Yoshino, Tomonori,Togo, Hideo
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p. 517 - 519
(2007/10/03)
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- Surfactant-stabilized aqueous iridium(0) colloidal suspension: An efficient reusable catalyst for hydrogenation of arenes in biphasic media
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Aqueous suspensions of iridium nanoparticles produced by the chemical reduction of IrCl3 assisted by sonication, in the presence of N,N-dimethyl-N-cetyl-N-(2-hydroxyethyl)ammonium chloride salt as surfactant, have shown an efficient activity for the catalytic hydrogenation of various aromatic derivatives in biphasic media under mild conditions. These nanocatalysts can be reused for further runs with a total conservation of activity and provided significant catalytic lifetime for anisole hydrogenation in pure water with 3000 total turnover (TTO).
- Mevellec, Vincent,Roucoux, Alain,Ramirez, Esther,Philippot, Karine,Chaudret, Bruno
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- Environmentally friendly esterification of carboxylic acids with triethyl orthoacetate in ionic liquid
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An operationally simple, inexpensive, efficient, and environmentally friendly esterification of carboxylic acids with triethyl orthoacetate under neutral conditions in a typical room temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate, was carried out to provide the corresponding ethyl esters in high yields.
- Yoshino, Tomonori,Togo, Hideo
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p. 1604 - 1606
(2007/10/03)
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- Al2O3/MeSO3H (AMA) as a new reagent with high selective ability for monoesterification of diols
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A new facile method for monoesterification of diols has been developed. A variety of diols, in particular oligoethylene glycols, were selectively monoesterified in excellent yields by reaction with aromatic and aliphatic acids in the presence of Al2O3/MeSO3H as a new reagent without use of any solvents.
- Sharghi, Hashem,Sarvari, Mona Hosseini
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p. 3627 - 3633
(2007/10/03)
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- A Simple and Efficient Esterification Method
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A convenient and practical esterification was realized and this reaction proceeded without a dehydrating reagent or water removal equipment. The synthesis of esters by reaction of carboxylic acids with various alcohols such as methyl, ethyl, isopropyl, isobutyl, allyl, benzyl, propargyl and decanyl alcohols were achieved with a catalytic amount of CBr4 under refluxing reaction condition.
- Ming-Yi, Chen,Lee, Adam Shih-Yuan
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p. 103 - 108
(2007/10/03)
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- Dimethylmalonyltrialkylphosphoranes: New general reagents for esterification reactions allowing controlled inversion or retention of configuration on chiral alcohols
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A new class of trialkylphosphorane has been prepared through reaction of a trialkylphosphine with 2-chlorodimethylmalonate in the presence of triethylamine. These new reagents promote the condensation reaction of carboxylic acids with alcohols to provide esters along with trialkylphosphine oxide and dimethylmalonate. The condensation reaction of chiral secondary alcohols can be controlled to give either high levels of inversion or retention through a subtle interplay involving basicity of the reaction media, solvent, and tuning the electronic and steric nature of the carboxylic acid and steric nature of the phosphorane employed. A coherent mechanism is postulated to explain these observations involving reaction via an initial acyloxyphosphonium ion.
- McNulty, James,Capretta, Alfredo,Laritchev, Vladimir,Dyck, Jeff,Robertson, Al J.
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p. 1597 - 1600
(2007/10/03)
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- Arene Hydrogenation with a Stabilised Aqueous Rhodium(0) Suspension: A Major Effect of the Surfactant Counter-Anion
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A reduced aqueous colloidal suspension of rhodium shows an efficient activity in the catalytic hydrogenation of various benzene derivatives under biphasic conditions at room temperature and under atmospheric hydrogen pressure. The rhodium nanoparticles in the size range of 2-2.5 nm have been synthesised by reducing RhCl3 · 3 H2O with sodium borohydride and were stabilised by highly water-soluble N,N-dimethyl-N-cetyl-N-(2- hydroxyethyl)ammonium salts (HEA16X, X = Br, Cl, I, CH3SO 3, BF4). The major influence of the counter-ion of these surfactants on catalytic activity and recycling is described. The best results have been obtained with chloride ammonium salts HEA16Cl.
- Roucoux, Alain,Schulz, Jürgen,Patin, Henri
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p. 222 - 229
(2007/10/03)
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- PHOSPHORANES AS COUPLING AGENTS AND THEIR PREPARATION
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Provided is a use as a coupling agent for condensation reactions of a compound of formula (I): wherein each of R1, R2, and R3 is independently H, hydrocarbyl, or hydrocarbyloxy, provided that not more than one of R1, R2, and R3 is H ; and at least one of Y1 and Y2 is an electron-withdrawing group and the other, if not an electron-withdrawing group, is H or a group that has no electron-donating properties, with the proviso that when one of Y1 and Y2 is H, the other is not -CN. Some of the compounds of formula (I) are novel, and methods of their preparation are also provided.
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