- Ceria supported Ru0-Ruδ+ clusters as efficient catalyst for arenes hydrogenation
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Selective hydrogenation of aromatic amines, especially chemicals such as aniline and bis(4-aminocyclohexyl)methane for non-yellowing polyurethane, is of particular interests due to the extensive applications. To conquer the existing difficulties in selective hydrogenation, the Ru0-Ruδ+/CeO2 catalyst with solid frustrated Lewis pairs was developed for aromatic amines hydrogenation with excellent activity and selectivity under relative milder conditions. The morphology, electronic and chemical properties, especially the Ru0-Ruδ+ clusters and reducible ceria were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electronic microscopy (SEM), X-ray photoelectron spectroscopy (XPS), CO2 temperature programmed desorption (CO2-TPD), H2 temperature programmed reduction (H2-TPR), H2 diffuse reflectance Fourier transform infrared spectroscopy (H2-DRIFT), Raman, etc. The 2% Ru/CeO2 catalyst exhibited good conversion of 95% and selectivity greater than 99% toward cyclohexylamine. The volcano curve describing the activity and Ru state was found. Owning to the “acidic site isolation” by surrounding alkaline sites, condensation between the neighboring amine molecules could be effectively suppressed. The catalyst also showed good stability and applicability for other aromatic amines and heteroarenes containing different functional groups.
- Cao, Yanwei,Zheng, Huan,Zhu, Gangli,Wu, Haihong,He, Lin
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supporting information
p. 770 - 774
(2020/08/24)
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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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-
- Zirconium-hydride-catalyzed site-selective hydroboration of amides for the synthesis of amines: Mechanism, scope, and application
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Developing mild and efficient catalytic methods for the selective synthesis of amines is a longstanding research objective. In this respect, catalytic deoxygenative amide reduction has proven to be promising but challenging, as this approach necessitates selective C–O bond cleavage. Herein, we report the selective hydroboration of primary, secondary, and tertiary amides at room temperature catalyzed by an earth-abundant-metal catalyst, Zr-H, for accessing diverse amines. Various readily reducible functional groups, such as esters, alkynes, and alkenes, were well tolerated. Furthermore, the methodology was extended to the synthesis of bio- and drug-derived amines. Detailed mechanistic studies revealed a reaction pathway entailing aldehyde and amido complex formation via an unusual C–N bond cleavage-reformation process, followed by C–O bond cleavage.
- Han, Bo,Jiao, Haijun,Wu, Lipeng,Zhang, Jiong
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p. 2059 - 2067
(2021/09/02)
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- Deoxygenative hydroboration of primary, secondary, and tertiary amides: Catalyst-free synthesis of various substituted amines
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Transformation of relatively less reactive functional groups under catalyst-free conditions is an interesting aspect and requires a typical protocol. Herein, we report the synthesis of various primary, secondary, and tertiary amines through hydroboration of amides using pinacolborane under catalyst-free and solvent-free conditions. The deoxygenative hydroboration of primary and secondary amides proceeded with excellent conversions. The comparatively less reactive tertiary amides were also converted to the corresponding N,N-diamines in moderate yields under catalyst-free conditions, although alcohols were obtained as a minor product.
- An, Duk Keun,Jaladi, Ashok Kumar,Kim, Hyun Tae,Yi, Jaeeun
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- Method for preparing primary amine by catalytically reducing nitrile compounds through nano-porous palladium catalyst
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The invention belongs to the technical field of heterogeneous catalysis, and provides a method for preparing primary amine by catalytically reducing nitrile compounds with a nano-porous palladium catalyst. According to the invention, aromatic and aliphatic nitrile compounds are adopted as raw materials, nano-porous palladium is adopted as a catalyst, ammonia borane is adopted as a hydrogen source, no additional additive is added, and selective hydrogenation is performed to prepare the corresponding primary amine. The method provided by the invention has the beneficial effects of mild reaction conditions, no additive, environmental protection, no need of hydrogen, simple operation, stable hydrogen source, safety, harmlessness, high conversion rate, high selectivity and good catalyst stability, and makes industrialization possible.
- -
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Paragraph 0097-0100
(2021/05/29)
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- SUPPORTED HETEROGENEOUS CATALYST, PREPARATION AND USE THEREOF
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A supported heterogeneous catalyst comprises rhodium and vanadium on a support, wherein the supported heterogeneous catalyst is preparable by depositing vanadium on a supported rhodium catalyst by impregnation. A process for preparing the aforementioned catalyst and a process for converting an amide into an amine in the presence of the aforementioned catalyst are provided.
- -
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Page/Page column 22
(2021/06/11)
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- Efficient hydrogenation of aliphatic amides to amines over vanadium-modified rhodium supported catalyst
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This work presents a highly efficient catalytic hydrogenation system developed for the selective transformation of tertiary N,N-dimethyldodecanamide and secondary azepan-2-one amides to the corresponding amines. Industrial hydrogenation catalysts Pd/Al2O3, Pt/Al2O3 and Rh/Al2O3 were modified with vanadium (V) or molybdenum (Mo) species as oxophilic centres. The modified catalysts were prepared by deposition of V or Mo precursor on supported catalysts via impregnation method. The catalysts were characterized by ICP-OES, XRD, XPS, H2-TPR, FTIR, CO-chemisorption, TEM, SEM-EDX and TGA. Modified Rh-V/Al2O3 catalyst displayed the best performance affording high yield and selectivity >95 % to the desired tertiary and secondary amines at moderate reaction conditions of T H2 0 sites and oxophilic Vδ+ sites in the bimetallic Rh-V/Al2O3 catalyst were determined to be beneficial for the selective dissociation of C[dbnd]O bond of the carboxamides into the desired amines.
- Hernandez, Willinton Y.,Kusema, Bright T.,Pennetier, Alex,Streiff, Stéphane
-
-
- 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.
-
supporting information
p. 5105 - 5114
(2020/08/25)
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- A State-of-the-Art Heterogeneous Catalyst for Efficient and General Nitrile Hydrogenation
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Cobalt-doped hybrid materials consisting of metal oxides and carbon derived from chitin were prepared, characterized and tested for industrially relevant nitrile hydrogenations. The optimal catalyst supported onto MgO showed, after pyrolysis at 700 °C, magnesium oxide nanocubes decorated with carbon-enveloped Co nanoparticles. This special structure allows for the selective hydrogenation of diverse and demanding nitriles to the corresponding primary amines under mild conditions (e.g. 70 °C, 20 bar H2). The advantage of this novel catalytic material is showcased for industrially important substrates, including adipodinitrile, picolinonitrile, and fatty acid nitriles. Notably, the developed system outperformed all other tested commercial catalysts, for example, Raney Nickel and even noble-metal-based systems in these transformations.
- Formenti, Dario,Mocci, Rita,Atia, Hanan,Dastgir, Sarim,Anwar, Muhammad,Bachmann, Stephan,Scalone, Michelangelo,Junge, Kathrin,Beller, Matthias
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supporting information
p. 15589 - 15595
(2020/10/02)
-
- Nickel(ii) and nickel(0) complexes as precursors of nickel nanoparticles for the catalytic hydrogenation of benzonitrile
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The use of the nickel(ii) complex [(TEEDA)NiCl2] (1; TEEDA= N,N,N′,N′-tetraethyl-ethylendiamine) and nickel(0) complex [Ni(COD)2] (5) as pre-catalysts in the additive-free catalytic hydrogenation of benzonitrile (BN) is reported. In the presence of 1 (1 mol%), BN was hydrogenated under relatively mild reaction conditions (100 °C, 120 psi H2, 72 h) to the corresponding secondary imine, N-benzylidenebenzylamine (BBA), in very good yield (83%). As a counterpart, 5 (1 mol%) selectively hydrogenated BN to benzylamine (BA) in excellent yield (96%) under similar reaction conditions (80 °C, 120 psi H2, 24 h). In both cases, nickel nanoparticles (Ni-NPs) were identified as the catalytically active species. These Ni-NPs were formed in situ from 1 and 5 without external additives or additional stabilizers. The use of complex 5 was extended to the hydrogenation of different (hetero) aromatic and aliphatic nitriles.
- Rodríguez, Alejandro A.,Gardu?o, Jorge A.,García, Juventino J.
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p. 1082 - 1089
(2020/01/31)
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- A cobalt phosphide catalyst for the hydrogenation of nitriles
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The study of metal phosphide catalysts for organic synthesis is rare. We present, for the first time, a well-defined nano-cobalt phosphide (nano-Co2P) that can serve as a new class of catalysts for the hydrogenation of nitriles to primary amines. While earth-abundant metal catalysts for nitrile hydrogenation generally suffer from air-instability (pyrophoricity), low activity and the need for harsh reaction conditions, nano-Co2P shows both air-stability and remarkably high activity for the hydrogenation of valeronitrile with an excellent turnover number exceeding 58000, which is over 20- to 500-fold greater than that of those previously reported. Moreover, nano-Co2P efficiently promotes the hydrogenation of a wide range of nitriles, which include di- and tetra-nitriles, to the corresponding primary amines even under just 1 bar of H2 pressure, far milder than the conventional reaction conditions. Detailed spectroscopic studies reveal that the high performance of nano-Co2P is attributed to its air-stable metallic nature and the increase of the d-electron density of Co near the Fermi level by the phosphidation of Co, which thus leads to the accelerated activation of both nitrile and H2. Such a phosphidation provides a promising method for the design of an advanced catalyst with high activity and stability in highly efficient and environmentally benign hydrogenations. This journal is
- Jitsukawa, Koichiro,Mitsudome, Takato,Mizugaki, Tomoo,Nakata, Ayako,Sheng, Min,Yamasaki, Jun
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p. 6682 - 6689
(2020/08/24)
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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 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.
- -
-
Paragraph 0027-0030; 0051-0055
(2020/05/30)
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- Cobalt-Nanoparticles Catalyzed Efficient and Selective Hydrogenation of Aromatic Hydrocarbons
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The development of inexpensive and practical catalysts for arene hydrogenations is key for future valorizations of this general feedstock. Here, we report the development of cobalt nanoparticles supported on silica as selective and general catalysts for such reactions. The specific nanoparticles were prepared by assembling cobalt-pyromellitic acid-piperazine coordination polymer on commercial silica and subsequent pyrolysis. Applying the optimal nanocatalyst, industrial bulk, substituted, and functionalized arenes as well as polycyclic aromatic hydrocarbons are selectively hydrogenated to obtain cyclohexane-based compounds under industrially viable and scalable conditions. The applicability of this hydrogenation methodology is presented for the storage of H2 in liquid organic hydrogen carriers.
- Murugesan, Kathiravan,Senthamarai, Thirusangumurugan,Alshammari, Ahmad S.,Altamimi, Rashid M.,Kreyenschulte, Carsten,Pohl, Marga-Martina,Lund, Henrik,Jagadeesh, Rajenahally V.,Beller, Matthias
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p. 8581 - 8591
(2019/09/12)
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- Method for preparing primary amines through hydrogen transfer selective nitrile reduction
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The invention discloses a method for preparing primary amines through hydrogen transfer selective nitrile reduction. The method includes the step of adding low-price copper, iron and other metal saltsor low-price easy-to-obtain iodine elementary substances as additives with a nitrile compound as the raw material and oxazole borane as the hydrogen transfer agent under the mild conditions, therebypromoting the hydrogen transfer reaction and selectively synthesizing a series of corresponding primary amines under different conditions respectively. The high yield and high selectivity are achievedin the reaction. The oxazole borane is obtained through reaction of alkamine and a tetrahydrofuran complex of borane. In addition, the method is mild in reaction condition, easy to operate, free of high-pressure devices, environmentally friendly and high in raw material general applicability, the agents required for the reaction are all low in price and easy to obtain, the reduction product is only primary amines, and selectivity and repeatability are high. Thus, an effective scheme is provided for the industrial production of other high-additional-value compounds of similar structures in future.
- -
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Paragraph 0062-0066
(2019/05/02)
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- Facile synthesis of supported Ru-Triphos catalysts for continuous flow application in selective nitrile reduction
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The selective catalytic hydrogenation of nitriles represents an important but challenging transformation for many homogeneous and heterogeneous catalysts. Herein, we report the efficient and modular solid-phase synthesis of immobilized Triphos-type ligands in very high yields, involving only minimal work-up procedures. The corresponding supported ruthenium-Triphos catalysts are tested in the hydrogenation of various nitriles. Under mild conditions and without the requirement of additives, the tunable supported catalyst library provides selective access to both primary amines and secondary imines. Moreover, the first application of a Triphos-type catalyst in a continuous flow process is presented demonstrating high catalyst life-time over at least 195 hours without significant activity loss.
- Konrath, Robert,Heutz, Frank J.L.,Steinfeldt, Norbert,Rockstroh, Nils,Kamer, Paul C.J.
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p. 8195 - 8201
(2019/09/19)
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- Continuous-Flow Hydrogenation and Reductive Deuteration of Nitriles: a Simple Access to α,α-Dideutero Amines
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A simple and efficient continuous flow methodology has been developed for hydrogenation and reductive deuteration of nitriles to yield primary amines and also valuable α,α-dideutero analogues. Raney nickel proved to be a useful catalyst for the transformation of a wide range of nitriles under reasonably mild conditions with excellent deuterium incorporation (>90 %) and quantitative conversion. Among known model compounds, three new deuterated primary amines were prepared. The large-scale synthesis of deuterated tryptamine was also carried out to deliver 1.1 g product under flow conditions.
- Mészáros, Rebeka,Peng, Bai-Jing,?tv?s, Sándor B.,Yang, Shyh-Chyun,Fül?p, Ferenc
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p. 1508 - 1511
(2019/11/03)
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- Synthesis of Secondary Aldimines from the Hydrogenative Cross-Coupling of Nitriles and Amines over Al2O3-Supported Ni Catalysts
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A heterogeneous Ni catalyst was discovered to be active in the synthesis of secondary cross-imines via hydrogenative coupling of nitriles and amines. The mesoporous Al2O3-supported Ni nanoparticles (abbreviated as Ni/m-Al2O3-600, where 600 represents the reduction temperature) were active in hydrogenative coupling of nitriles and amines reaction at 80 °C and 1 bar H2, affording corresponding cross-imines with yields in the range 64.1-98.1%. Density functional theory calculations reveal the hydrogenation of benzonitrile (PhCN) to benzylamine (PhCH2NH2) has higher activation energy than that for hydrogenative cross-coupling of PhCN and RNH2 on the Ni/m-Al2O3-600 catalyst, suggesting the latter reaction is more favorable. The theoretical calculations are in good agreement with our experimental results.
- Zhou, Peng,Jiang, Liang,Wang, Shuguo,Hu, Xun,Wang, Hongming,Yuan, Ziliang,Zhang, Zehui
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p. 8413 - 8423
(2019/09/07)
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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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- Nitrogen-Doped Carbon-Supported Nickel Nanoparticles: A Robust Catalyst to Bridge the Hydrogenation of Nitriles and the Reductive Amination of Carbonyl Compounds for the Synthesis of Primary Amines
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An efficient method was developed for the synthesis of primary amines either from the hydrogenation of nitriles or reductive amination of carbonyl compounds. The reactions were catalyzed by nitrogen-doped mesoporous carbon (MC)-supported nickel nanoparticles (abbreviated as MC/Ni). The MC/Ni catalyst demonstrated high catalytic activity for the hydrogenation of nitriles into primary amines in high yields (81.9–99 %) under mild reaction conditions (80 °C and 2.5 bar H2). The MC/Ni catalyst also promoted the reductive amination of carbonyl compounds for the synthesis of primary amines at 80 °C and 1 bar H2. The hydrogenation of nitriles and the reductive amination proceeded through the same intermediates for the generation of the primary amines. To the best of our knowledge, no other heterogeneous non-noble metal catalysts have been reported for the synthesis of primary amines under mild conditions, both from the hydrogenation of nitriles and reductive amination.
- Zhang, Yangmin,Yang, Hanmin,Chi, Quan,Zhang, Zehui
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p. 1246 - 1255
(2019/03/07)
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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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- Reusable Nickel Nanoparticles-Catalyzed Reductive Amination for Selective Synthesis of Primary Amines
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The preparation of nickel nanoparticles as efficient reductive amination catalysts by pyrolysis of in situ generated Ni-tartaric acid complex on silica is presented. The resulting stable and reusable Ni-nanocatalyst enables the synthesis of functionalized and structurally diverse primary benzylic, heterocyclic and aliphatic amines starting from inexpensive and readily available carbonyl compounds and ammonia in presence of molecular hydrogen. Applying this Ni-based amination protocol, -NH2 moiety can be introduced in structurally complex compounds, for example, steroid derivatives and pharmaceuticals.
- Murugesan, Kathiravan,Beller, Matthias,Jagadeesh, Rajenahally V.
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supporting information
p. 5064 - 5068
(2019/03/19)
-
- 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)
-
- 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)
-
- Selective Synthesis of Primary Amines from Nitriles under Hydrogenation Conditions
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The hydrogenation of aliphatic nitriles over Pd/C, Pd/Al2O3, and Pd?Au/Al2O3 catalysts were evaluated for the selective hydrogenation of aliphatic nitriles to the corresponding primary amines. The highest selectivity (>99%) toward primary amines was achieved when the reaction was carried out in acetic acid using 10 mol% of 25% Pd-5% Au/Al2O3 under relatively low hydrogen pressure (0.8 MPa). Characterization of the catalysts by XRD, CO adsorption experiments, and EXAFS revealed that the excellent selectivity of 25% Pd-5% Au/Al2O3 toward the synthesis of primary amines is determined by the electronic properties and/or the surface structure resulting from alloying Pd with Au. (Figure presented.).
- Yoshimura, Masatoshi,Komatsu, Akira,Niimura, Masaru,Takagi, Yukio,Takahashi, Tohru,Ueda, Shun,Ichikawa, Tomohiro,Kobayashi, Yutaka,Okami, Hiroki,Hattori, Tomohiro,Sawama, Yoshinari,Monguchi, Yasunari,Sajiki, Hironao
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p. 1726 - 1732
(2018/03/21)
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- Highly Stable COF-Supported Co/Co(OH)2 Nanoparticles Heterogeneous Catalyst for Reduction of Nitrile/Nitro Compounds under Mild Conditions
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Ordered nanoporosity in covalent organic framework (COF) offers excellent opportunity for property development. Loading nanoparticles (nPs) onto them is one approach to introducing tailor-made properties into a COF. Here, a COF–Co/Co(OH)2 composite containing about 16 wt% of 2 nPs is prepared on a N-rich COF support that catalyzes the release of theoretical equivalence of H2 from readily available, safe, and cheap NaBH4. Furthermore, the released H2 is utilized for the hydrogenation of nitrile and nitro compounds to amines under ambient conditions in a facile one-pot reaction. The COF “by choice” is built from “methoxy” functionalized dialdehydes which is crucial in enabling the complete retention of the COF structure under the conditions of the catalysis, where the regular Schiff bonds would have hydrolyzed. The N-rich binding pockets in the COF ensure strong nP–COF interactions, which provides stability and enables catalyst recycling. Modeling studies reveal the crucial role played by the COF in exposing the active facets and thereby in controlling the activation of the reducing agent. Additionally, via density functional theory, we provide a rational explanation for how these COFs can stabilize nanoparticles which grow beyond the limiting pore size of the COF and yet result in a truly stable heterogeneous catalyst – a ubiquitous observation. The study underscores the versatility of COF as a heterogeneous support for developing cheap and highly active nonnoble metal catalysts.
- Mullangi, Dinesh,Chakraborty, Debanjan,Pradeep, Anu,Koshti, Vijay,Vinod, Chathakudath P.,Panja, Soumendranath,Nair, Sunil,Vaidhyanathan, Ramanathan
-
-
- 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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- Anticancer Activity and Catalytic Potential of Ruthenium(II)-Arene Complexes with N,O-Donor Ligands
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The special ability of organometallic complexes to catalyze various transformations might offer new effective mechanisms for the treatment of cancer. Studies that report both the biological properties and the ability of metallic complexes to promote therapeutically relevant catalytic reactions are limited. Herein, we report the anticancer activity and catalytic potential of some ruthenium(II)-arene complexes bearing bidentate Schiff base ligands (2a and 2b) and their reduced analogues (5a and 5b, respectively). In comparison to their Schiff base counterparts 2a and 2b, we demonstrate that amine complexes 5a and 5b display (i) a higher in vitro antiproliferative activity on different human cancer cell lines, (ii) a lower rate of hydrolysis, and (iii) an improved initial catalytic rate for the reduction of NAD+ to NADH. In contrast to their imine analogues 2a and 2b, we also show that amine complexes 5a and 5b induce the generation of intracellular reactive oxygen species (ROS) in MCF-7 breast cancer cells. Our results highlight the impact that a simple ligand modification such as the reduction of an imine moiety can have on both the catalytic and biological activities of metal complexes. Moreover, the ruthenium complexes reported here display some antiproliferative activity against T47D breast cancer cells, known for their cis-platin resistance.
- Haghdoost, Mohammad Mehdi,Guard, Juliette,Golbaghi, Golara,Castonguay, Annie
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supporting information
p. 7558 - 7567
(2018/07/10)
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- Selective hydrogenation of amides to alcohols in water solvent over a heterogeneous CeO2-supported Ru catalyst
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CeO2-supported Ru (Ru/CeO2) worked as an effective and reusable heterogeneous catalyst for the selective dissociation of the C-N bond in amides, particularly primary amides, with H2 in water solvent at low reaction temperature of 333 K, and high yields of the corresponding alcohols were obtained from primary amides.
- Tamura, Masazumi,Ishikawa, Susumu,Betchaku, Mii,Nakagawa, Yoshinao,Tomishige, Keiichi
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p. 7503 - 7506
(2018/07/13)
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- Corresponding amine nitrile and method of manufacturing thereof
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The invention relates to a manufacturing method of nitrile. Compared with the prior art, the manufacturing method has the characteristics of significantly reduced using amount of an ammonia source, low environmental pressure, low energy consumption, low production cost, high purity and yield of a nitrile product and the like, and nitrile with a more complex structure can be obtained. The invention also relates to a method for manufacturing corresponding amine from nitrile.
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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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- Cobalt-Catalyzed and Lewis Acid-Assisted Nitrile Hydrogenation to Primary Amines: A Combined Effort
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The selective hydrogenation of nitriles to primary amines using a bench-stable cobalt precatalyst under 4 atm of H2 is reported herein. The catalyst precursor was reduced in situ using NaHBEt3, and the resulting Lewis acid formed, BEt3, was found to be integral to the observed catalysis. Mechanistic insights gleaned from para-hydrogen induced polarization (PHIP) transfer NMR studies revealed that the pairwise hydrogenation of nitriles proceeded through a Co(I/III) redox process.
- Tokmic, Kenan,Jackson, Bailey J.,Salazar, Andrea,Woods, Toby J.,Fout, Alison R.
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supporting information
p. 13554 - 13561
(2017/10/05)
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- Catalytic Hydrogenation of Arenes in Water Over In Situ Generated Ruthenium Nanoparticles Immobilized on Carbon
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We describe a tandem process to generate active Ru nanoparticles (≈7 nm) immobilised in situ on carbon from an organometallic precursor and formic acid to afford the hydrogenation of a wide range of arenes and heteroarenes in yields up to 72 % with high conversions and selectivities for the desired products. The hydrogenation of several substrates analogous to lignin-derived fragments to the corresponding alicyclic products was also achieved. Our experimental investigations evidenced that the observed enhanced activity for arene hydrogenation was driven by the unique structural advantages of the organometallic precursor to activate formic acid, in which the presence of a nitrogen ligand is crucial to achieve a high catalytic activity. TEM analysis revealed the formation of Ru0 nanoparticles, and Hg0 poisoning experiments support the heterogeneous nature of the active catalyst.
- Dwivedi, Ambikesh Dhar,Rai, Rohit Kumar,Gupta, Kavita,Singh, Sanjay Kumar
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p. 1930 - 1938
(2017/06/13)
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- Catalyst-Dependent Selective Hydrogenation of Nitriles: Selective Synthesis of Tertiary and Secondary Amines
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In the presence of palladium on carbon (Pd/C) as a catalyst, hydrogenation of aliphatic nitriles in cyclohexane efficiently proceeded at 25-60 °C under ordinary hydrogen gas pressure to afford the corresponding tertiary amines. However, the use of rhodium on carbon (Rh/C) led to the highly selective generation of secondary amines. Hydrogenation of aromatic nitriles and cyclohexanecarbonitrile selectively produced secondary amines in the presence of either Pd/C or Rh/C.
- Monguchi, Yasunari,Mizuno, Masahiro,Ichikawa, Tomohiro,Fujita, Yuki,Murakami, Eri,Hattori, Tomohiro,Maegawa, Tomohiro,Sawama, Yoshinari,Sajiki, Hironao
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p. 10939 - 10944
(2017/10/27)
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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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- 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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- Selective hydrogenation of nitriles to primary amines catalyzed by a novel iron complex
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Hydrogenation of nitriles to primary amines constitutes an atom-efficient and environmentally benign synthetic reaction. Herein we present a novel complex based on earth-abundant iron, and its application in the catalytic homogeneous hydrogenation of (hetero)aromatic, benzylic, and aliphatic nitriles to selectively form primary amines.
- Chakraborty, Subrata,Leitus, Gregory,Milstein, David
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supporting information
p. 1812 - 1815
(2016/02/05)
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- Selective catalytic hydrogenation of nitriles to primary amines using iron pincer complexes
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The selective catalytic hydrogenation of nitriles to primary amines with the well-defined Fe(PNPCy) pincer complex 2 is reported. This iron pincer catalyst shows superior catalytic activity and selectivity in the reduction of various nitriles including industrially relevant adipodinitrile in high yields under relatively mild conditions.
- Lange,Elangovan,Cordes,Spannenberg,Jiao,Junge,Bachmann,Scalone,Topf,Junge,Beller
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p. 4768 - 4772
(2016/07/11)
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- Stable and Inert Cobalt Catalysts for Highly Selective and Practical Hydrogenation of C≡N and C=O Bonds
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Novel heterogeneous cobalt-based catalysts have been prepared by pyrolysis of cobalt complexes with nitrogen ligands on different inorganic supports. The activity and selectivity of the resulting materials in the hydrogenation of nitriles and carbonyl compounds is strongly influenced by the modification of the support and the nitrogen-containing ligand. The optimal catalyst system ([Co(OAc)2/Phenα-Al2O3]-800 = Cat. E) allows for efficient reduction of both aromatic and aliphatic nitriles including industrially relevant dinitriles to primary amines under mild conditions. The generality and practicability of this system is further demonstrated in the hydrogenation of diverse aliphatic, aromatic, and heterocyclic ketones as well as aldehydes, which are readily reduced to the corresponding alcohols.
- Chen, Feng,Topf, Christoph,Radnik, J?rg,Kreyenschulte, Carsten,Lund, Henrik,Schneider, Matthias,Surkus, Annette-Enrica,He, Lin,Junge, Kathrin,Beller, Matthias
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supporting information
p. 8781 - 8788
(2016/08/02)
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- Selective Catalytic Hydrogenations of Nitriles, Ketones, and Aldehydes by Well-Defined Manganese Pincer Complexes
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Hydrogenations constitute fundamental processes in organic chemistry and allow for atom-efficient and clean functional group transformations. In fact, the selective reduction of nitriles, ketones, and aldehydes with molecular hydrogen permits access to a green synthesis of valuable amines and alcohols. Despite more than a century of developments in homogeneous and heterogeneous catalysis, efforts toward the creation of new useful and broadly applicable catalyst systems are ongoing. Recently, Earth-abundant metals have attracted significant interest in this area. In the present study, we describe for the first time specific molecular-defined manganese complexes that allow for the hydrogenation of various polar functional groups. Under optimal conditions, we achieve good functional group tolerance, and industrially important substrates, e.g., for the flavor and fragrance industry, are selectively reduced.
- Elangovan, Saravanakumar,Topf, Christoph,Fischer, Steffen,Jiao, Haijun,Spannenberg, Anke,Baumann, Wolfgang,Ludwig, Ralf,Junge, Kathrin,Beller, Matthias
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supporting information
p. 8809 - 8814
(2016/07/29)
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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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- Catalytic Hydrogenation for the Preparation of Amines from Amide Acetals, Ketene N,O-Acetals or Ester Imides
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The present invention relates to a process for the preparation of amines, comprising the following steps: Reaction of a (i) amide acetal of the general formula (I), or (ii) ketene N,O-acetal of the general formula (II), or (iii) ester imide of the general formula (III) with H2 in the presence of a hydrogenation catalyst, where catalyst and amide acetal or ketene N,O-acetal or ester imide are used in a molar ratio of from 1:10 to 1:100 000 and where a hydrogen pressure of from 0.1 bar to 200 bar is established and where a temperature in the range of from 0° C. to 250° C. is established.
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Paragraph 0149
(2016/10/04)
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- Rhodium-catalyzed electrochemical hydrodefluorination: A mild approach for the degradation of fluoroaromatic pollutants
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Many fluoroorganic compounds are toxic and persistent, and achieving their efficient degradation under mild conditions is currently a challenge. Herein, we developed a new electrochemical hydrodefluorination (HDF) system based on rhodium electrocatalyst for the degradation of fluoroaromatic (FA) pollutants. The HDF system realized the rapid degradation of 18 representative FAs to form nonfluorinated organics and F- under mild conditions (room temperature and pressure, water medium, air atmosphere, without the use of hazardous reagents). This study may provide a new promising alternative for the practical treatment of waste water containing FA pollutants.
- Xu, Yinghua,Ma, Hongxing,Ge, Tingjie,Chu, Youqun,Ma, Chun-An
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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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- Integrated Heterogeneous Metal/Enzymatic Multiple Relay Catalysis for Eco-Friendly and Asymmetric Synthesis
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Organic synthesis is in general performed using stepwise transformations where isolation and purification of key intermediates is often required prior to further reactions. Herein we disclose the concept of integrated heterogeneous metal/enzymatic multiple relay catalysis for eco-friendly and asymmetric synthesis of valuable molecules (e.g., amines and amides) in one-pot using a combination of heterogeneous metal and enzyme catalysts. Here reagents, catalysts, and different conditions can be introduced throughout the one-pot procedure involving multistep catalytic tandem operations. Several novel cocatalytic relay sequences (reductive amination/amidation, aerobic oxidation/reductive amination/amidation, reductive amination/kinetic resolution and reductive amination/dynamic kinetic resolution) were developed. They were next applied to the direct synthesis of various biologically and optically active amines or amides in one-pot from simple aldehydes, ketones, or alcohols, respectively.
- Palo-Nieto, Carlos,Afewerki, Samson,Anderson, Mattias,Tai, Cheuk-Wai,Berglund, Per,Córdova, Armando
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p. 3932 - 3940
(2016/07/06)
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- Selective Hydrogenation of Nitriles to Primary Amines Catalyzed by a Cobalt Pincer Complex
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The catalytic hydrogenation of nitriles to primary amines represents an atom-efficient and environmentally benign reduction methodology in organic chemistry. This has been accomplished in recent years mainly with precious-metal-based catalysts, with a single exception. Here we report the first homogeneous Co-catalyzed hydrogenation of nitriles to primary amines. Several (hetero)aromatic, benzylic, and aliphatic nitriles undergo hydrogenation to the corresponding primary amines in good to excellent yields under the reaction conditions.
- Mukherjee, Arup,Srimani, Dipankar,Chakraborty, Subrata,Ben-David, Yehoshoa,Milstein, David
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supporting information
p. 8888 - 8891
(2015/08/03)
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- Hydrogenation of Aliphatic and Aromatic Nitriles Using a Defined Ruthenium PNP Pincer Catalyst
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Selective catalytic reductions of nitriles are presented using the commercially available Ru-Macho-BH complex. A variety of aliphatic, aromatic and (hetero)cyclic nitriles including industrially important adipodinitrile are hydrogenated to the corresponding primary amines. Modelling suggests the reaction follows an outer sphere hydrogenation mechanism. An efficient and selective catalytic reduction of nitriles is presented using the commercially available Ru-Macho-BH complex. A variety of aliphatic, aromatic and (hetero)cyclic nitriles including the industrially important adipodinitrile are hydrogenated to the corresponding primary amines. The reaction follows an outer-sphere mechanism.
- Neumann, Jacob,Bornschein, Christoph,Jiao, Haijun,Junge, Kathrin,Beller, Matthias
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supporting information
p. 5944 - 5948
(2015/09/22)
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- HIV INTEGRASE INHIBITORS
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The present invention features compounds that are HIV integrase inhibitors and therefore are useful in the inhibition of HIV replication, the prevention and/or treatment of infection by HIV, and in the treatment of AIDS and/or ARC.
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- Ruthenium/imidazolylphosphine catalysis: Hydrogenation of aliphatic and aromatic nitriles to form amines
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A convenient and efficient catalyst system for the hydrogenation of aliphatic nitriles towards the corresponding primary amines in high to excellent yields is presented. In addition, aromatic nitriles are reduced smoothly, too. The use of low catalyst loadings and molecular hydrogen make this protocol an attractive methodology. It's not complicated: A general and easy homogeneous catalyst system based on [Ru(cod)(methylallyl)2] and a cyclohexyl-substituted imidazolylphosphine ligand for selective hydrogenation of aliphatic nitriles is presented. In addition, by using an isopropyl-substituted imidazolylphosphine ligand, selected aromatic nitriles were reduced with excellent yields towards the primary amine. Furthermore, two new crystal structures give an insight of possible pre-catalysts.
- Werkmeister, Svenja,Junge, Kathrin,Wendt, Bianca,Spannenberg, Anke,Jiao, Haijun,Bornschein, Christoph,Beller, Matthias
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supporting information
p. 4227 - 4231
(2014/05/06)
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- Homogeneous hydrogenation of nitriles catalyzed by molybdenum and tungsten amides
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Low-valent molybdenum and tungsten amides M(NO)(CO)(PNP) {M = Mo, 1a; W, 1b; PNP = N(CH2CH2PiPr2) 2} were found to be active catalysts for the hydrogenation of various nitriles to the corresponding imines, primary amines, and N-substituted imines with high selectivity for the latter type of product. A wide range of p-and m-substituted aromatic nitriles-p-methyl, p-methoxy, p-bromobenzonitriles; 3-trifluoromethylbenzonitrile, m-and p-disubstituted benzonitrile; the heterocyclic 2-thiophencarbonitrile; and the aliphatic nitriles cyclohexylcarbonitrile and benzylcyanide-could be hydrogenated at 140 °C and 60 bar H2 in THF with high yields. TOFs were found to be between 0.4 and 36 h-1.
- Chakraborty, Subrata,Berke, Heinz
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p. 2191 - 2194
(2014/07/21)
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