- Cs2CO3-promoted efficient carbonate and carbamate synthesis on solid phase
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Mild and efficient preparation of alkyl carbonates and carbamates on solid supports is described herein. Alcohols or amines were coupled with Merrifield's resin through a CO2 linker in the presence of cesium carbonate and tetrabutylammonium iodide (TBAI).
- Salvatore, Ralph N.,Flanders, Vincent L.,Ha, Dang,Jung, Kyung Woon
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Read Online
- Self-assembly and characterization of a novel hydrogen-bonded nanostructure
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A novel hydrogen-bonded supramolecular system of a [60]fullerene derivative with perylene bisimide was synthesized and characterized. 1H NMR spectra confirmed the existence of strong hydrogen-bonding interaction between compounds 1 and 5. Transmission electron microscopy images of 1-5 aggregates showed spherical particles having a mean diameter of 50 nm. The photocurrent response of the film was measured, and a steady and rapid anodic photocurrent response was obtained.
- Liu, Yang,Xiao, Shengqiang,Li, Hongmei,Li, Yuliang,Liu, Huibiao,Lu, Fushen,Zhuang, Junpeng,Zhu, Daoben
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- Reduction of azides to amines with borohydride exchange resin - Nickel acetate
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Borohydride exchange resin (BER) - nickel acetate system in methanol readily reduces both aliphatic and aromatic azides to the corresponding amines in excellent yields.
- Yoon,Choi,Shon
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Read Online
- Direct terminal alkylamino-functionalization via multistep biocatalysis in one recombinant whole-cell catalyst
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Direct and regiospecific amino-functionalization of non-activated carbon could be achieved using one recombinant microbial catalyst. The presented proof of concept shows that heterologous pathway engineering allowed the construction of a whole-cell biocatalyst catalyzing the terminal amino-functionalization of fatty acid methyl esters (e.g., dodecanoic acid methyl ester) and alkanes (e.g., octane). By coupling oxygenase and transaminase catalysis in vivo, both substrates are converted with absolute regiospecificity to the terminal amine via two sequential oxidation reactions followed by an amination step. Such demanding chemical three-step reactions achieved with a single catalyst demonstrate the tremendous potential of whole-cell biocatalysts for the production of industrially relevant building blocks. Copyright
- Schrewe, Manfred,Ladkau, Nadine,Buehler, Bruno,Schmid, Andreas
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- Testing of microorganisms for ω-transaminase activity
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Various bacterial cells were tested to identify ω-transaminase activity. For this purpose, the kinetic resolution of a rac-amine was chosen as an assay reaction transforming, in the ideal case, one enantiomer into the corresponding ketone and leaving the other enantiomer untouched. Sodium pyruvate was employed as an amino acceptor. To test also for the amination of the prochiral ketone various amino donors were investigated. Alanine proved to be the most suitable amino donor especially when coupled with a pyruvate decarboxylase to shift the reaction equilibrium; however, much lower conversions were achieved compared to the kinetic resolution. Janibacter terrae DSM 13953 was identified as the most suitable microorganism to possess ω-transaminase activity.
- Clay, Dorina,Koszelewski, Dominik,Grischek, Barbara,Gross, Johannes,Lavandera, Ivan,Kroutil, Wolfgang
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- Kinetic studies of the Hydrolysis of n-Octylamine on the Surface of a Sodium Dodecyl Sulfate Micelle by the Ultrasonic Absorption Method
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Ultrasonic relaxation absorption has been observed in aqueous solution of n-octylamine (OA) in the presence of micelles of sodium dodecyl sulfate (SDS).From various experiments changing (i) the concentrations of OA and SDS, (ii) the alkyl-chain length of the detergent and amine, (iii) the pH of the solution, and (iv) the type of detergent, the relaxation absorption has been ascribed to the hydrolysis of OA on the surface of the SDS micelle: C8H17NH3+ + OH- C8H17NH2 + H2O.The forward (kf) and backward (kb) rate constants, the apparent equilibrium constant (K), and the volume change (ΔV) for the hydrolysis have been determined to be γ2kf = 5.5*108 M-1 s-1, kb = 1.2*107 s-1, K (=γ2kf/kb) = 45 M-1, and ΔV = 26.5 cm3 mol-1 at 20 deg C, respectively, where γ is the mean ionic activity coefficient.The values of γ2kf and K were found to be smaller than the corresponding values in the absence of the micelle by a factor of about 1/50.These micellar effects have been interpreted in terms of electrostatic interactions between the micelle and OH- and OA+ ions.
- Yamashita, Teruyo,Yano, Hiroshige,Harada, Shoji,Yasunaga, Tatsuya
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- Highly selective synthesis of primary amines from amide over Ru-Nb2O5 catalysts
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Amines are an important class of compounds in natural products and medicines. The universal availability of amides provides a potential way for the synthesis of amines. Herein, Ru/Nb2O5 catalyst is demonstrated to be highly efficient and stable for the selective hydrogenation of propionamide to propylamine (as a model reaction), with up to 91.4% yield of propylamine under relatively mild conditions. Results from XPS analyses, CO chemisorption, TEM images and DRIFTS spectra revealed that the unique properties of Nb2O5 can effectively activate the C=O group of amides, and the smaller Ru particles on Nb2O5 could further promote the activation, leading to superior catalytic performance of Ru/Nb2O5 for amide hydrogenation. Meanwhile, reducing the surface acidity of Nb2O5 can greatly inhibit the side reactions to by-products, and further enhance the selectivity to amine. Moreover, this catalytic system is also applicable for the hydrogenation of a variety of amides and provides high potential for the industrial production of primary amines from amides.
- Guo, Wanjun,Guo, Yong,Jia, Hongyan,Liu, Xiaohui,Pan, Hu,Wang, Yangang,Wang, Yanqin,Xia, Qineng
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- Hydroboration of Nitriles, Esters, and Carbonates Catalyzed by Simple Earth-Abundant Metal Triflate Salts
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During the past decade earth-abundant metals have become increasingly important in homogeneous catalysis. One of the reactions in which earth-abundant metals have found important applications is the hydroboration of unsaturated C?C and C?X bonds (X=O or N). Within these set of transformations, the hydroboration of challenging substrates such as nitriles, carbonates and esters still remain difficult and often relies on elaborate ligand designs and highly reactive catalysts (e. g., metal alkyls/hydrides). Here we report an effective methodology for the hydroboration of challenging C≡N and C=O bonds that is simple and applicable to a wide set of substrates. The methodology is based on using a manganese(II) triflate salt that, in combination with commercially available potassium tert-butoxide and pinacolborane, catalyzes the hydroboration of nitriles, carbonates, and esters at room temperature and with near quantitative yields in less than three hours. Additional studies demonstrated that other earth-abundant metal triflate salts can facilitate this reaction as well, which is further discussed in this report.
- Thenarukandiyil, Ranjeesh,Satheesh, Vanaparthi,Shimon, Linda J. W.,de Ruiter, Graham
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p. 999 - 1006
(2021/03/30)
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- PROCESS FOR PRODUCING A CATALYST, CATALYST AND USE THEREOF
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A process for producing a supported catalyst comprising metal nanoparticles, said process comprises the following steps: (a) preparing a supported catalyst comprising metal nanoparticles; (b) peducing the catalyst of step (a); (c) treating the reduced catalyst of step (b) with at least one alcohol, and (d) calcining the treated catalyst of step (c) to remove carbon species, to produce said supported catalyst. A catalyst obtainable from this process can be used in amination, hydrogenation, dehydrogenation, hydrogenolysis and aerobic oxidation reactions.
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Page/Page column 13-15; 17
(2021/06/26)
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- Indirect reduction of CO2and recycling of polymers by manganese-catalyzed transfer hydrogenation of amides, carbamates, urea derivatives, and polyurethanes
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The reduction of polar bonds, in particular carbonyl groups, is of fundamental importance in organic chemistry and biology. Herein, we report a manganese pincer complex as a versatile catalyst for the transfer hydrogenation of amides, carbamates, urea derivatives, and even polyurethanes leading to the corresponding alcohols, amines, and methanol as products. Since these compound classes can be prepared using CO2as a C1 building block the reported reaction represents an approach to the indirect reduction of CO2. Notably, these are the first examples on the reduction of carbamates and urea derivatives as well as on the C-N bond cleavage in amides by transfer hydrogenation. The general applicability of this methodology is highlighted by the successful reduction of 12 urea derivatives, 26 carbamates and 11 amides. The corresponding amines, alcohols and methanol were obtained in good to excellent yields up to 97%. Furthermore, polyurethanes were successfully converted which represents a viable strategy towards a circular economy. Based on control experiments and the observed intermediates a feasible mechanism is proposed.
- Liu, Xin,Werner, Thomas
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p. 10590 - 10597
(2021/08/20)
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- PROCESS FOR CATALYTIC AMINATION OF ALCOHOL
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A process for catalytic amination of an alcohol, involving a catalyst comprising Co-based catalyst, wherein said catalyst comprises at least one promoter selected from the group consisting of metals having a melting point of 350℃ or less and any mixtures thereof.
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Page/Page column 9; 10
(2021/06/26)
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- Direct Enzymatic Synthesis of Fatty Amines from Renewable Triglycerides and Oils
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Fatty amines represent an important class of commodity chemicals which have broad applicability in different industries. The synthesis of fatty amines starts from renewable sources such as vegetable oils or animal fats, but the process has multiple drawbacks that compromise the overall effectiveness and efficiency of the synthesis. Herein, we report a proof-of-concept biocatalytic alternative towards the synthesis of primary fatty amines from renewable triglycerides and oils. By coupling a lipase with a carboxylic acid reductase (CAR) and a transaminase (TA), we have accomplished the direct synthesis of multiple medium and long chain primary fatty amines in one pot with analytical yields as high as 97 %. We have also performed a 75 mL preparative scale reaction for the synthesis of laurylamine from trilaurin, obtaining 73 % isolated yield.
- Bevinakatti, Han,Citoler, Joan,Finnigan, William,Turner, Nicholas J.
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- Catalytic Hydrogenation of Urea Derivatives and Polyureas
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We present herein the catalytic hydrogenation of various urea derivatives to amines and methanol. The reaction is catalyzed by a ruthenium or an iridium Macho pincer complex and produces amine and methanol in very good to excellent yields. Moreover, we also expand this concept to demonstrate the first example of the hydrogenative depolymerization of polyureas to produce diamines and methanol in moderate yields.
- Kumar, Amit,Luk, James
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supporting information
p. 4546 - 4550
(2021/08/30)
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- Heterogeneous photocatalysis of azides: Extending nitrene photochemistry to longer wavelengths
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The photodecomposition of azides to generate nitrenes usually requires wavelengths in the 300 nm region. In this study, we show that this reaction can be readily performed in the UVA region (368 nm) when catalyzed by Pd-decorated TiO2. In aqueous medium the reaction leads to amines, with water acting as the H source; however, in non-protic and non-nucleophilic media, such as acetonitrile, nitrenes recombine to yield azo compounds, while azirine-mediated trapping occurs in the presence of nucleophiles. The heterogeneous process facilitates catalyst separation while showing great chemoselectivity and high yields.
- Argüello, Juan E.,Lanterna, Anabel E.,Lemir, Ignacio D.,Scaiano, Juan C.
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supporting information
p. 10239 - 10242
(2020/10/02)
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- Process for synthesis of n-octylamine using loop reactor
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The invention relates to the technical field of n-octylamine synthesis, in particular to a method for synthesizing n-octylamine by using a loop reactor. The invention relates to a method for synthesizing n-octylamine by using a loop reactor, which comprises the following step of: reacting n-caprylic acid, liquid ammonia and hydrogen serving as raw materials in the loop reactor. By adopting a special ammoniation catalyst, the ammoniation reaction temperature is remarkably reduced, so that corrosion to a pipeline is effectively prevented; in addition, the method is high in conversion rate, goodin selectivity, low in reaction temperature, small in corrosion to equipment, low in raw material cost, small in three-waste pollution and suitable for industrial production of n-octylamine.
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Paragraph 0053-0080
(2021/01/04)
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- One-pot reductive amination of carboxylic acids: a sustainable method for primary amine synthesis
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The reductive amination of carboxylic acids is a very green, efficient and sustainable method for the production of (bio-based) amines. However, with current technology, this reaction requires two to three reaction steps. Here, we report the first (heterogeneous) catalytic system for the one-pot reductive amination of carboxylic acids to amines, with solely H2 and NH3 as the reactants. This reaction can be performed with relatively cheap ruthenium-tungsten bimetallic catalysts in the green and benign solvent cyclopentyl methyl ether (CPME). Selectivities of up to 99% for the primary amine could be achieved at high conversions. Additionally, the catalyst is recyclable and tolerant for common impurities such as water and cations (e.g. sodium carboxylate).
- Coeck, Robin,De Vos, Dirk E.
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supporting information
p. 5105 - 5114
(2020/08/25)
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- Ambient-Temperature Synthesis of Primary Amines via Reductive Amination of Carbonyl Compounds
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Efficient synthesis of primary amines via low-temperature reductive amination of carbonyl compounds using NH3 and H2 as the nitrogen and hydrogen resources is highly desired and challenging in the chemistry community. Herein, we employed naturally occurring phytic acid as a renewable precursor to fabricate titanium phosphate (TiP)-supported Ru nanocatalysts with different reduction degrees of RuO2 (Ru/TiP-x, x represents the reduction temperature) by combining ball milling and molten-salt processes. Very interestingly, the obtained Ru/TiP-100 had good catalytic performance for the reductive amination of carbonyl compounds at ambient temperature, resulting from the synergistic cooperation of the support (TiP) and the Ru/RuO2 with a suitable proportion of Ru0 (52%). Various carbonyl compounds could be efficiently converted into the corresponding primary amines with high yields. More importantly, the conversion of other substrates with reducible groups could also be achieved at ambient temperature. Detailed investigations indicated that the partially reduced Ru and the support (TiP) were indispensable. The high activity and selectivity of Ru/TiP-100 catalyst originates from the relatively high acidity and the suitable electron density of metallic Ru0.
- Xie, Chao,Song, Jinliang,Hua, Manli,Hu, Yue,Huang, Xin,Wu, Haoran,Yang, Guanying,Han, Buxing
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p. 7763 - 7772
(2020/08/21)
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- Facile synthesis of controllable graphene-co-shelled reusable Ni/NiO nanoparticles and their application in the synthesis of amines under mild conditions
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The primary objective of many researchers in chemical synthesis is the development of recyclable and easily accessible catalysts. These catalysts should preferably be made from Earth-abundant metals and have the ability to be utilised in the synthesis of pharmaceutically important compounds. Amines are classified as privileged compounds, and are used extensively in the fine and bulk chemical industries, as well as in pharmaceutical and materials research. In many laboratories and in industry, transition metal catalysed reductive amination of carbonyl compounds is performed using predominantly ammonia and H2. However, these reactions usually require precious metal-based catalysts or RANEY nickel, and require harsh reaction conditions and yield low selectivity for the desired products. Herein, we describe a simple and environmentally friendly method for the preparation of thin graphene spheres that encapsulate uniform Ni/NiO nanoalloy catalysts (Ni/NiO?C) using nickel citrate as the precursor. The resulting catalysts are stable and reusable and were successfully used for the synthesis of primary, secondary, tertiary, and N-methylamines (more than 62 examples). The reaction couples easily accessible carbonyl compounds (aldehydes and ketones) with ammonia, amines, and H2 under very mild industrially viable and scalable conditions (80 °C and 1 MPa H2 pressure, 4 h), offering cost-effective access to numerous functionalized, structurally diverse linear and branched benzylic, heterocyclic, and aliphatic amines including drugs and steroid derivatives. We have also demonstrated the scale-up of the heterogeneous amination protocol to gram-scale synthesis. Furthermore, the catalyst can be immobilized on a magnetic stirring bar and be conveniently recycled up to five times without any significant loss of catalytic activity and selectivity for the product.
- Cui, Zhibing,Liu, Jianguo,Liu, Qiying,Ma, Longlong,Singh, Thishana,Wang, Chenguang,Wang, Nan,Zhu, Yuting
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supporting information
p. 7387 - 7397
(2020/11/19)
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- METHOD FOR PRODUCING AN AMINE
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The invention relates to a method for producing an amine by reacting an alcohol, aldehyde and/or ketone with hydrogen and nitrogen-containing compound in the presence of a silver and/or ruthenium promoted cobalt catalyst. The nitrogen-containing compound is selected from ammonia, primary amines and secondary amines.
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Page/Page column 13-15
(2020/06/05)
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- Effects of ruthenium hydride species on primary amine synthesis by direct amination of alcohols over a heterogeneous Ru catalyst
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Heterogeneously catalysed synthesis of primary amines by direct amination of alcohols with ammonia has long been an elusive goal. In contrast to reported Ru-based catalytic systems, we report that Ru-MgO/TiO2 acts as an effective heterogeneous catalyst for the direct amination of a variety of alcohols to primary amines at low temperatures of ca. 100 °C without the introduction of H2 gas. The present system could be applied to a variety of alcohols and provides an efficient synthetic route for 2,5-bis(aminomethyl)furan (BAMF), an attention-getting biomonomer. The high catalytic performance can be rationalized by the reactivity tuning of Ru-H species using MgO. Spectroscopic measurements suggest that MgO enhances the reactivity of hydride species by electron donation from MgO to Ru.
- Hara, Michikazu,Kamata, Keigo,Kita, Yusuke,Kuwabara, Midori,Yamadera, Satoshi
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p. 9884 - 9890
(2020/10/06)
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- A multifaceted role of a mobile bismuth promoter in alcohol amination over cobalt catalysts
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Promotion with small amounts of different elements is an efficient strategy for the enhancement of the performance of many heterogeneous catalysts. Supported cobalt catalysts exhibit significant activity in the synthesis of primary amines via alcohol amination with ammonia, which is an economically efficient and environmentally friendly process. Insufficient selectivity to primary amines, low activity and fast cobalt catalyst deactivation remain serious issues restricting the application of alcohol amination in the industry. In this work, we have discovered the multifaceted role of the bismuth promoter, which is highly mobile under reaction conditions, in 1-octanol amination over supported cobalt catalysts. First, the overall reaction rate was enhanced more than twice on promotion with bismuth. Second, the selectivity to primary amines increased 6 times in the presence of Bi at high alcohol conversion. Finally, the bismuth promotion resulted in extremely high stability of the cobalt catalyst. Characterization by XRD, temperature programmed reduction, STEM, CO chemisorption, BET, TGA and FTIR has showed that the enhancement of the catalytic performance on promotion with bismuth is due to better cobalt reducibility, easy removal of strongly adsorbed intermediates and products by the mobile promoter and suppression of amine coupling reactions resulting in secondary and tertiary amines.
- Bahri, Mounib,Ersen, Ovidiu,Khodakov, Andrei Y.,Kusema, Bright T.,Niu, Feng,Ordomsky, Vitaly V.,Yan, Zhen
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supporting information
p. 4270 - 4278
(2020/07/14)
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- Method for preparing primary amine by catalyzing reductive amination of aldehyde ketone compounds
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The invention discloses a method for preparing primary amine by catalyzing reductive amination of aldehyde ketone compounds. The method comprises the following steps: 1) mixing nickel nitrate hexahydrate, citric acid and an organic solvent, carrying out heating and stirring until a colloidal material is obtained, drying the colloidal material, roasting the colloidal material in a protective atmosphere, pickling, washing and drying a roasted product, and performing a partial oxidation reaction on a dried product in an oxygen-nitrogen mixed atmosphere to obtain a catalyst for a reductive amination reaction; and 2) mixing aldehyde or ketone compounds, a methanol solution of ammonia and the reductive amination reaction catalyst, introducing hydrogen, and carrying out a reductive amination reaction. The method has the advantages of high primary amine yield, high selectivity, wide aldehyde ketone substrate range, short reaction time, mild reaction conditions, low cost, greenness, economicalperformance and the like; the used reductive amination reaction catalyst can be recycled more than 10 times, and the catalytic activity of the catalyst is not obviously changed in gram-level reactions; and the method is suitable for large-scale application.
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Paragraph 0027-0030; 0051-0055
(2020/05/30)
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- PROCESS FOR PREPARING PRIMARY AMINES FROM ALCOHOLS
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A process for preparing a primary amine by reacting an alcohol with ammonia in the present of a metal catalyst comprising metal nanoparticles, wherein the metal nano-particles comprises at least one transition metal in elemental form and/or at least one transition metal compound and carbonaceous species are deposited on the metal nan-oparticles.
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Page/Page column 13
(2020/06/10)
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- Anti-Markovnikov Hydroamination of Alkenes with Aqueous Ammonia by Metal-Loaded Titanium Oxide Photocatalyst
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A completely new route was established to synthesize valuable primary amines from alkenes by using aqueous ammonia, that is, a simple photocatalytic hydroamination of alkenes using aqueous ammonia with a metal-loaded TiO2 photocatalyst. Although the photochemical hydroamination prefers to form amines according to the Markovnikov rule, the new photocatalytic hydroamination gives anti-Markovnikov products predominantly. With an Au-loaded TiO2 photocatalyst, the amine yield reached up to 93% and the regioselectivity of anti-Markovnikov products was above 98%. The reaction mechanism was proposed for the new photocatalytic hydroamination.
- Park, Soyeong,Jeong, Jaeyoung,Fujita, Ken-Ichi,Yamamoto, Akira,Yoshida, Hisao
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supporting information
p. 12708 - 12714
(2020/08/21)
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- Amination of aliphatic alcohols with urea catalyzed by ruthenium complexes: effect of supporting ligands
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In the present study, ruthenium-catalyzed amination of alcohols by urea as a convenient ammonia carrier in the presence of free diphosphine ligands has been described. A number of ruthenium-phosphine complexes have been studied among which, [(Cp)RuCl(dppe)] was found as an efficient catalyst for alcohol amination reaction. The crystal structures of two new half-sandwich ruthenium complexes, [(Cp)RuCl(dppe)] and [(C6H6)RuCl2(PHEt2)], were determined by X-ray crystallographic analysis. Also the effect of using different supporting phosphines, ratio of raw materials and reaction temperature on conversion and selectivity was investigated. Under optimum reaction conditions high conversion (98percent) and chemo-selectivity toward secondary amines were obtained.
- Dindar, Sara,Nemati Kharat, Ali
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- A biocatalytic cascade for the conversion of fatty acids to fatty amines
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Fatty amine synthesis from renewable sources is an energetically-demanding process involving toxic metal catalysts and harsh reaction conditions as well as selectivity problems. Herein we present a mild, biocatalytic alternative to the conventional amination of fatty acids through a one-pot tandem cascade performed by a carboxylic acid reductase (CAR) and a transaminase (ω-TA). Saturated and unsaturated fatty acids, with carbon chain lengths ranging from C6 to C18, were successfully aminated obtaining conversions of up to 96%.
- Citoler, Joan,Derrington, Sasha R.,Galman, James L.,Bevinakatti, Han,Turner, Nicholas J.
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supporting information
p. 4932 - 4935
(2019/09/30)
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- Na2S-promoted reduction of azides in water: Synthesis of pyrazolopyridines in one pot and evaluation of antimicrobial activity
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Reduction of various azides using Na2S has been accomplished in water, and, in situ, the resulting amines on reaction with various ketones lead to pyrazolo[3,4-b]pyridines in one pot. Thus, a number of new trifluoromethyl-substituted pyrazolo[3,4-b]pyridine compounds have been prepared and screened for antimicrobial activity against different Gram-positive and Gram-negative strains. A good number of compounds, 4a, 4b, 4d, 4f, 4i, 4k, 4l, 4m, 4r and 4s, were found to possess promising activity. Notably, Na2S on hydrolysis in water generates H2S and NaOH, which facilitate the reduction of azides followed by intramolecular cyclization leading to the title compounds. To the best of our knowledge, this is the first report of the synthesis of the title compounds in aqueous medium in a one-pot reaction.
- Kale, Ashok,Medishetti, Nagaraju,Kanugala, Sirisha,Ganesh Kumar,Atmakur, Krishnaiah
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p. 3186 - 3194
(2019/03/26)
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- Deacetylative Amination of Acetyl Arenes and Alkanes with C-C Bond Cleavage
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The Br?nsted acid-catalyzed synthesis of primary amines from acetyl arenes and alkanes with C-C bond cleavage is described. Although the conversion from an acetyl group to amine has traditionally required multiple steps, the method described herein, which uses an oxime reagent as an amino group source, achieves the transformation directly via domino transoximation/Beckmann rearrangement/Pinner reaction. The method was also applied to the synthesis of γ-aminobutyric acids, such as baclophen and rolipram.
- Hyodo, Kengo,Hasegawa, Genna,Maki, Hiroya,Uchida, Kingo
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supporting information
p. 2818 - 2822
(2019/04/25)
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- Nanoceria-promoted low Pd-Ni catalyst for the synthesis of secondary amines from aliphatic alcohols and ammonia
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This paper describes the preparation of a series of bimetallic Pd-Ni catalysts supported over nanoceria with very low Ni and Pd loading (2-TPR, H2-TPD, STEM-EDS-SDD and XPS. The sequence of impregnation of both metals and the Pd loading affected to an important extent the catalytic activity by conditioning the crystallite size and the Pd and Ni speciation, as well as the reducibility and reversible H2 storage properties. By optimizing the preparation protocols, a 0.5wt% Pd-0.5wt% Ni-Pd/CeO2 formulation prepared by sequential impregnation of the nickel and palladium precursors afforded 80% yield of dioctylamine at almost full conversion [TON = 1160 mmol per mmol (Ni + Pd)surface] in the direct amination reaction of 1-octanol with ammonia at 180 °C for 2 h. Metal leaching during the reaction could be completely avoided. The high catalytic performance of Pd-Ni induced by nanoceria places this catalyst among the best ever reported catalysts for the synthesis of secondary amines.
- Fang,Yan,Vits,Southward,Pera-Titus
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p. 1215 - 1230
(2019/03/12)
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- METHOD FOR AMINATION OF ALCOHOL
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A method for the amination of an alcohol comprising contacting the alcohol with NH 3 and H 2 in the presence of a catalyst is described. A method of preparing metallic ruthenium nanoparticles of controllable size and the use of metallic ruthenium nanoparticles as catalyst for the amination of an alcohol with NH 3 and furthermore are described.
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Page/Page column 7-8
(2019/12/28)
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- TETRADENTATE LIGAND, AND PRODUCTION METHOD THEREFOR, SYNTHETIC INTERMEDIATE THEREOF, AND TRANSITION METAL COMPLEX THEREOF
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The present invention relates to: a compound as a ligand in a variety of catalytic organic synthetic reactions; a method for producing the compound; a synthetic intermediate of the compound; and a transition metal complex which has the compound as a ligand. The compound includes a compound represented by the following general formula (1A):
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Paragraph 0287-0292
(2019/05/15)
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- Sustainable hydrogenation of aliphatic acyclic primary amides to primary amines with recyclable heterogeneous ruthenium-tungsten catalysts
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The hydrogenation of amides is a straightforward method to produce (possibly bio-based) amines. However current amide hydrogenation catalysts have only been validated in a rather limited range of toxic solvents and the hydrogenation of aliphatic (acyclic) primary amides has rarely been investigated. Here, we report the use of a new and relatively cheap ruthenium-tungsten bimetallic catalyst in the green and benign solvent cyclopentyl methyl ether (CPME). Besides the effect of the Lewis acid promotor, NH3 partial pressure is identified as the key parameter leading to high primary amine yields. In our model reaction with hexanamide, yields of up to 83% hexylamine could be achieved. Beside the NH3 partial pressure, we investigated the effect of the catalyst support, PGM-Lewis acid ratio, H2 pressure, temperature, solvent tolerance and product stability. Finally, the catalyst was characterized and proven to be very stable and highly suitable for the hydrogenation of a broad range of amides.
- Coeck, Robin,Berden, Sarah,De Vos, Dirk E.
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supporting information
p. 5326 - 5335
(2019/10/11)
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- Selective Transformations of Triglycerides into Fatty Amines, Amides, and Nitriles by using Heterogeneous Catalysis
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The use of triglycerides as an important class of biomass is an effective strategy to realize a more sustainable society. Herein, three heterogeneous catalytic methods are reported for the selective one-pot transformation of triglycerides into value-added chemicals: i) the reductive amination of triglycerides into fatty amines with aqueous NH3 under H2 promoted by ZrO2-supported Pt clusters; ii) the amidation of triglycerides under gaseous NH3 catalyzed by high-silica H-beta (Hβ) zeolite at 180 °C; iii) the Hβ-promoted synthesis of nitriles from triglycerides and gaseous NH3 at 220 °C. These methods are widely applicable to the transformation of various triglycerides (C4–C18 skeletons) into the corresponding amines, amides, and nitriles.
- Jamil, Md. A. R.,Siddiki, S. M. A. Hakim,Touchy, Abeda Sultana,Rashed, Md. Nurnobi,Poly, Sharmin Sultana,Jing, Yuan,Ting, Kah Wei,Toyao, Takashi,Maeno, Zen,Shimizu, Ken-ichi
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p. 3115 - 3125
(2019/04/26)
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- Preparation of nitrogen-doped carbon supported cobalt catalysts and its application in the reductive amination
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The use of non-noble metal catalysts with high activity is of great importance for organic transformations. Herein, nitrogen-doped carbon supported cobalt catalysts with high surface area up to 981.2 m2/g were prepared via the simple pyrolysis of cobalt coordinated organic polymers with silica as the hard template. The pyrolysis temperature showed a great effect on the structure and properties of the as-prepared catalysts. The Co@NC-800 catalyst with the pyrolysis temperature of 800 °C demonstrated a high activity for the selective reductive amination of carbonyl compounds to primary amines with ammonia and hydrogen. Structurally-diverse primary amines with yields in the range from 81.8% to 100% were attained under the optimal conditions. The Co@NC-800 catalyst could be reused without the loss of its activity. The Co@NC-800 catalyst demonstrated comparable activity as the reported heterogeneous noble metal catalysts.
- Yuan, Ziliang,Liu, Bing,Zhou, Peng,Zhang, Zehui,Chi, Quan
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p. 347 - 356
(2019/01/24)
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- Highly efficient nitrobenzene and alkyl/aryl azide reduction in stainless steel jars without catalyst addition
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The mechanochemical and selective reduction of aryl nitro and aryl/alkyl azide derivatives, with either formate salts or hydrazine, to the corresponding, synthetically useful amines occurs in excellent yields in a planetary ball mill without the addition of a catalyst. This newly developed and solvent-free protocol is efficient, fast and does not require the addition of a metal hydrogenation catalyst as the stainless steel jar itself fulfils that role. The method has been applied to a broad range of compounds and excellent yields have been obtained. The formylation of alkyl amines has been successfully performed, by means of mechanochemical activation, in the presence of ammonium formate alone.
- Martina, Katia,Baricco, Francesca,Tagliapietra, Silvia,Moran, Maria Jesus,Cravotto, Giancarlo,Cintas, Pedro
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supporting information
p. 18881 - 18888
(2018/11/26)
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- Visible-light-driven Efficient Photocatalytic Reduction of Organic Azides to Amines over CdS Sheet–rGO Nanocomposite
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CdS sheet–rGO nanocomposite as a heterogeneous photocatalyst enables visible-light-induced photocatalytic reduction of aromatic, heteroaromatic, aliphatic and sulfonyl azides to the corresponding amines using hydrazine hydrate as a reductant. The reaction shows excellent conversion and chemoselectivity towards the formation of the amine without self-photoactivated azo compounds. In the adopted strategy, CdS not only accelerates the formation of nitrene through photoactivation of azide but also enhances the decomposition of azide to a certain extent, which entirely suppressed formation of the azo compound. The developed CdS sheet-rGO nanocomposite catalyst is very active, providing excellent results under irradiation with a 40 W simple household CFL lamp.
- Singha, Krishnadipti,Mondal, Aniruddha,Ghosh, Subhash Chandra,Panda, Asit Baran
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p. 255 - 260
(2018/01/15)
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- Synthesis of cobalt nanoparticles by pyrolysis of Vitamin B12: A non-noble-metal catalyst for efficient hydrogenation of nitriles
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A facile preparation of vitamin B12-derived carbonaceous cobalt particles supported on ceria is reported. The resulting composite material is obtained upon wet impregnation of ceria with natural cyanocobalamin and consecutive pyrolysis under inert conditions. The novel catalyst shows good to excellent performance in the industrially relevant heterogeneous hydrogenation of nitriles to the corresponding primary amines.
- Ferraccioli, Raffaella,Borovika, Diana,Surkus, Annette-Enrica,Kreyenschulte, Carsten,Topf, Christoph,Beller, Matthias
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p. 499 - 507
(2018/02/07)
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- Cobalt-based nanoparticles prepared from MOF-carbon templates as efficient hydrogenation catalysts
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The development of efficient and selective nanostructured catalysts for industrially relevant hydrogenation reactions continues to be an actual goal of chemical research. In particular, the hydrogenation of nitriles and nitroarenes is of importance for the production of primary amines, which constitute essential feedstocks and key intermediates for advanced chemicals, life science molecules and materials. Herein, we report the preparation of graphene shell encapsulated Co3O4- and Co-nanoparticles supported on carbon by the template synthesis of cobalt-terephthalic acid MOF on carbon and subsequent pyrolysis. The resulting nanoparticles create stable and reusable catalysts for selective hydrogenation of functionalized and structurally diverse aromatic, heterocyclic and aliphatic nitriles, and as well as nitro compounds to primary amines (>65 examples). The synthetic and practical utility of this novel non-noble metal-based hydrogenation protocol is demonstrated by upscaling several reactions to multigram-scale and recycling of the catalyst.
- Murugesan, Kathiravan,Senthamarai, Thirusangumurugan,Sohail, Manzar,Alshammari, Ahmad S.,Pohl, Marga-Martina,Beller, Matthias,Jagadeesh, Rajenahally V.
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p. 8553 - 8560
(2018/11/30)
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- PROCESS FOR PREPARING AMINE VIA DIRECT AMINATION REACTION
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Disclosed is an effective process for converting alcohols to an amine, notably primary, with desired characteristics such as inexpensiveness, high selectivity and conversion. Specifically, the reaction is performed in the presence of a low loading transition metal catalyst, notably noble metal-free metal.
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Page/Page column 16-17
(2018/08/26)
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- PROCESS FOR PREPARING AN AMINE VIA A DIRECT AMINATION REACTION
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This invention provides a process for preparing an amine by direct amination of alcohols in the presence of CD assisted catalyst, notably permitting then to produce aliphatic amines by aliphatic alcohols.
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Page/Page column 14; 19
(2018/09/21)
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- Development of a novel protocol for chemoselective deprotection of N/O-benzyloxycarbonyl (Cbz) at ambient temperature
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Abstract: A novel protocol for the deprotection of N-benzyloxycarbonyl and O-benzyloxycarbonyl groups by nickel boride generated in situ from NaBH4 and NiCl2·6H2O in methanol at room temperature has been developed to give the corresponding amines and phenols. This protocol is chemoselective as groups like chloro, bromo, amide, ester, pyridine, and tert-butyloxycarbonyl moiety are unaffected under these conditions. The deprotection has also been validated in gram scale reactions, to establish the wider appropriateness of this protocol. Graphical abstract: [Figure not available: see fulltext.].
- Saroha, Mohit,Aggarwal, Komal,Bartwal, Gaurav,Khurana, Jitender M.
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p. 2231 - 2235
(2018/10/02)
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- Process for producing long chain amino acids and dibasic acids
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There is disclosed a process for the production of long chain amino acid and long chain dibasic acid, comprising: (1) reacting long chain keto fatty acid with hydroxylamine or subjecting keto fatty acid to an ammoximation reaction to yield an oxime fatty acid; (2) subjecting the oxime fatty acid to the Beckmann rearrangement to yield a mixture of two amide fatty acids; (3) hydrolyzing the mixed amide fatty acids to produce long chain amino acid, long chain dibasic acid, short chain alkylamine, and alkanoic acid.
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- An improved and one-pot procedure to the synthesis of symmetric amines by domino reactions of 5-methyl-1,3,4-thiadiazole-2-amine, a new nitrogen atom donor, and alkyl halides
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Abstract: A new one-pot method has been introduced in this work for the synthesis of symmetrical primary, secondary, and tertiary alkyl amines from alkyl halides and 5-methyl-1,3,4-thiadiazole-2-amine as a nitrogen-transfer reagent. In this method, all three types of amines have been successfully prepared after changing the ratio of substrates and base control. In addition to the introduction of a new nitrogen-transfer reagent, other important features of this work include normal atmospheric conditions and excellent yields under mild reaction conditions.
- Soleiman-Beigi, Mohammad,Mohammadi, Fariba
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p. 2123 - 2128
(2017/10/26)
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- Selective Hydrogenation of Nitriles to Primary Amines by using a Cobalt Phosphine Catalyst
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A general procedure for the catalytic hydrogenation of nitriles to primary amines by using a non-noble metal-based system is presented. Co(acac)3 in combination with tris[2-(dicyclohexylphosphino)ethyl]phosphine efficiently catalyzes the selective hydrogenation of a wide range of (hetero)aromatic and aliphatic nitriles to give the corresponding amines.
- Adam, Rosa,Bheeter, Charles Beromeo,Cabrero-Antonino, Jose R.,Junge, Kathrin,Jackstell, Ralf,Beller, Matthias
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p. 842 - 846
(2017/03/17)
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- A metagenomics approach for new biocatalyst discovery: Application to transaminases and the synthesis of allylic amines
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Transaminase enzymes have significant potential for the sustainable synthesis of amines using mild aqueous reaction conditions. Here a metagenomics mining strategy has been used for new transaminase enzyme discovery. Starting from oral cavity microbiome samples, DNA sequencing and bioinformatics analyses were performed. Subsequent in silico mining of a library of contiguous reads built from the sequencing data identified 11 putative Class III transaminases which were cloned and overexpressed. Several screening protocols were used and three enzymes selected of interest due to activities towards substrates covering a wide structural diversity. Transamination of functionalized cinnamaldehydes was then investigated for the production of valuable amine building blocks.
- Baud, Damien,Jeffries, Jack W. E.,Moody, Thomas S.,Ward, John M.,Hailes, Helen C.
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p. 1134 - 1143
(2017/08/14)
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- PRODUCTION OF AMINES UTILIZING ZEOLITE CATALYSTS
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The present invention concerns a process for forming a primary or a secondary amine via amination reaction comprising: reacting an alcohol with an amine in the presence of a zeolite comprising a transition metal chosen in the group consisting of Group 8 to 12 elements of the Periodic Table and any combination thereof.
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Page/Page column 14
(2017/09/27)
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- In vitro biocatalytic pathway design: Orthogonal network for the quantitative and stereospecific amination of alcohols
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The direct and efficient conversion of alcohols into amines is a pivotal transformation in chemistry. Here, we present an artificial, oxidation-reduction, biocatalytic network that employs five enzymes (alcohol dehydrogenase, NADP-oxidase, catalase, amine dehydrogenase and formate dehydrogenase) in two concurrent and orthogonal cycles. The NADP-dependent oxidative cycle converts a diverse range of aromatic and aliphatic alcohol substrates to the carbonyl compound intermediates, whereas the NAD-dependent reductive aminating cycle generates the related amine products with >99% enantiomeric excess (R) and up to >99% conversion. The elevated conversions stem from the favorable thermodynamic equilibrium (K′eq = 1.88 × 1042 and 1.48 × 1041 for the amination of primary and secondary alcohols, respectively). This biocatalytic network possesses elevated atom efficiency, since the reaction buffer (ammonium formate) is both the aminating agent and the source of reducing equivalents. Additionally, only dioxygen is needed, whereas water and carbonate are the by-products. For the oxidative step, we have employed three variants of the NADP-dependent alcohol dehydrogenase from Thermoanaerobacter ethanolicus and we have elucidated the origin of the stereoselective properties of these variants with the aid of in silico computational models.
- Knaus, Tanja,Cariati, Luca,Masman, Marcelo F,Mutti, Francesco G.
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p. 8313 - 8325
(2017/10/19)
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- Facile preparation of Ni/Al2O3 catalytic formulations with the aid of cyclodextrin complexes: Towards highly active and robust catalysts for the direct amination of alcohols
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A series of Ni/Al2O3 catalysts with variable Ni loading (2–20 wt%) were prepared by aqueous wet impregnation of a nitrate precursor using native cyclodextrins as metal complex hosts. The impact of β-CD was carefully characterized at different stages of the preparation by a set of complementary techniques including TG-MS analysis, mass spectrometry, X-ray diffraction, temperature-programmed reduction, CO pulse chemisorption, X-ray photoelectron spectroscopy and electron microscopy. It was found that the use of cyclodextrins afforded a much higher Ni dispersion and narrower distribution of Ni particle sizes, as well as a much higher availability of reduced surface Ni species. As a result, the cyclodextrin-assisted catalysts exhibited enhanced catalytic properties in the direct amination of benzyl alcohol with aniline and 1-octanol with ammonia, both operated via the hydrogen borrowing mechanism. Furthermore, the use of cyclodextrins allowed a significant improvement of the robustness of the catalysts by mitigating the nickel leaching during reaction.
- Tomer, Ajay,Wyrwalski, Frédéric,Przybylski, Cédric,Paul, Jean-Fran?ois,Monflier, Eric,Pera-Titus, Marc,Ponchel, Anne
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p. 111 - 124
(2017/11/03)
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- Mixed oxides supported low-nickel formulations for the direct amination of aliphatic alcohols with ammonia
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The present study focuses on the selective synthesis of primary amines from aliphatic alcohols and ammonia using alumina-ceria supported nickel formulations based on very low nickel loading (≤2 wt%) and without any additive or external H2 supply. The effect of the catalyst preparation methods and modes of nickel impregnation were studied in detail and comprehensively characterized. The best formulation afforded 80% n-octanol conversion with 78% selectivity to n-octylamine at optimized reaction conditions, which were far better than control catalysts and benchmark Ni-alumina formulations relying on high Ni loadings. The enhanced activities of the alumina-ceria supported nickel catalysts was attributed to three combined effects: (1) a higher reducibility of surface nickel oxide species, (2) the genesis of very small and homogeneously distributed nickel nanoparticles (2–3 nm), and (3) a strong decline in the formation of nickel aluminates. Furthermore, unlike benchmark Ni catalysts, these formulations afforded a higher resistance to leaching.
- Tomer,Yan,Ponchel,Pera-Titus
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p. 133 - 146
(2017/11/03)
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- Ruthenium-Catalyzed Deaminative Hydrogenation of Aliphatic and Aromatic Nitriles to Primary Alcohols
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The deaminative hydrogenation of nitriles towards alcohols is a useful reaction to transform nitriles into alcohols with NH3 as the sole byproduct. Using the simple and robust RuHCl(CO)(PPh3)3 complex as a catalyst, at low H2 pressures a series of aliphatic and aromatic nitriles could be transformed into the corresponding alcohols. Suitable solvent systems for these reactions were 1,4-dioxane/water and EtOH/water mixtures. In most cases, the selectivity for the alcohols was excellent, and the corresponding amines were formed only in trace amounts.
- Molnár, István Gábor,Calleja, Pilar,Ernst, Martin,Hashmi, A. Stephen K.,Schaub, Thomas
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p. 4175 - 4178
(2017/10/09)
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- Cyclodextrin-Grafted Silica-Supported Pd Nanoparticles: An Efficient and Versatile Catalyst for Ligand-Free C-C Coupling and Hydrogenation
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Silica is an extremely versatile support, which is capable of hosting metal nanoparticles (NPs) and enhancing their stability and reactivity. In this study, a novel cyclodextrin/silica support for Pd NPs, which we have denoted Pd/Si-CD, has been prepared. The highly efficient and homogeneous impregnation of small palladium nanoparticles on this support has been carried out under conventional conditions, and ultrasound irradiation has been shown to have a beneficial effect on catalyst preparation. The catalyst exhibited excellent activity in ligand-free C-C Suzuki and Heck couplings with a large number of aryl iodide and bromides, in which microwave irradiation use cuts down reaction time. Pd/Si-CD have shown high activity and selectivity in the hydrogenation reaction, and the semihydrogenation of phenyl acetylene was also studied with excellent results.
- Martina, Katia,Baricco, Francesca,Caporaso, Marina,Berlier, Gloria,Cravotto, Giancarlo
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p. 1176 - 1184
(2016/04/05)
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- NNP-Type Pincer Imidazolylphosphine Ruthenium Complexes: Efficient Base-Free Hydrogenation of Aromatic and Aliphatic Nitriles under Mild Conditions
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A series of seven novel NImNHP-type pincer imidazolylphosphine ruthenium complexes has been synthesized and fully characterized. The use of hydrogenation of benzonitrile as a benchmark test identified [RuHCl(CO)(NImNHPtBu)] as the most active catalyst. With its stable Ru-BH4 analogue, in which chloride is replaced by BH4, a broad range of (hetero)aromatic and aliphatic nitriles, including industrially interesting adiponitrile, has been hydrogenated under mild and base-free conditions.
- Adam, Rosa,Alberico, Elisabetta,Baumann, Wolfgang,Drexler, Hans-Joachim,Jackstell, Ralf,Junge, Henrik,Beller, Matthias
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p. 4991 - 5002
(2016/04/05)
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- A Mild and Base-Free Protocol for the Ruthenium-Catalyzed Hydrogenation of Aliphatic and Aromatic Nitriles with Tridentate Phosphine Ligands
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A novel protocol for the general hydrogenation of nitriles in the absence of basic additives is described. The system is based on the combination of [Ru(cod)(methylallyl)2] (cod=cyclooctadiene) and L2. A variety of aromatic and aliphatic nitriles is hydrogenated under mild conditions (50 °C and 15 bar H2) with this system. Kinetic studies revealed higher activity in the case of aromatic nitriles compared with aliphatic ones.
- Adam, Rosa,Bheeter, Charles Beromeo,Jackstell, Ralf,Beller, Matthias
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p. 1329 - 1334
(2016/04/20)
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- SYNTHESIS OF AMIDES AND AMINES FROM ALDEHYDES OR KETONES BY HETEROGENEOUS METAL CATALYSIS
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This invention concerns the first mild and efficient synthesis of primary amines and amides from aldehydes or ketones using a heterogeneous metal catalystand amine donor. The initial heterogeneous metal- catalyzed reaction between the carbonyl and the amine donor components is followed up with the addition of a suitable acylating agent component in one-pot. Hence, the present invention provides a novel catalytic one-pot three-component synthesis of amides. Moreover, the integration of enzyme catalysis allows for eco-friendly one-pot co-catalytic synthesis ofamides from aldehyde and ketone substrates, respectively. The process can be applied to the co-catalytic one-pot three-component synthesis of capsaicin and its analogues from vanillin or vanillyl alcohol. It can also be applied for asymmetric synthesis. In the present invention, a novel co-catalytic reductive amination/dynamic kinetic resolution (dkr) relay sequence for the asymmetric synthesis of optically active amides from ketones is disclosed. Moreover, implementation of a catalytic reductive amination/kinetic resolution (kr) relay sequence produces the corresponding optically active amide product and optical active primary amine product with the opposite stereochemistry from the starting ketones.
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Page/Page column 17
(2016/07/05)
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- The preparation obtained by homogeneous catalysis mellow amination method of the primary amine
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The invention relates to a method for producing primary amines comprising at least one functional group of formula (-CH2-NH2), by alcohol amination of educts which comprise at least one functional group of formula (-CH2-OH), using ammonia, and elimination of water. The homogeneously catalyzed alcohol amination is carried out in the presence of at least one complex catalyst which contains at least one element selected from the groups 8 and 9 of the periodic table and at least one phosphorus donor ligand of general formula (I).
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Paragraph 0207-0208; 0210
(2017/02/28)
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- A ruthenium racemisation catalyst for the synthesis of primary amines from secondary amines
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A Ru-based half sandwich complex used in amine and alcohol racemization reactions was found to be active in the splitting of secondary amines to primary amines using NH3. Conversions up to 80% along with very high selectivities were achieved. However, after about 80% conversion the catalyst lost activity. Similar to Shvo's catalyst, the complex might deactivate under the influence of ammonia. It was revealed that not NH3 but mainly the primary amine is responsible for the deactivation.
- Pingen, Dennis,Altinta?, ?i?dem,Rudolf Schaller, Max,Vogt, Dieter
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p. 11765 - 11771
(2016/07/28)
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