- In Situ Formation of Cationic π-Allylpalladium Precatalysts in Alcoholic Solvents: Application to C-N Bond Formation
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We report an efficient Buchwald-Hartwig cross-coupling reaction in alcoholic solvent, in which a low catalyst loading showed excellent performance for coupling aryl halides (I, Br, and Cl) with a broad set of amines, amides, ureas, and carbamates under mild conditions. Mechanistically speaking, in a protic and polar medium, extremely bulky biarylphosphine ligands interact with the dimeric precatalyst [Pd(π-(R)-allyl)Cl]2 to form the corresponding cationic complexes [Pd(π-(R)-allyl)(L)]Cl in situ and spontaneously. The resulting precatalyst further evolves under basic conditions into the corresponding L-Pd(0) catalyst, which is commonly employed for cross-coupling reactions. This mechanistic study highlights the prominent role of alcoholic solvents for the formation of the active catalyst.
- Bailly, Aurélien,Bihel, Frédéric,Grimaud, Laurence,Oliva, Estefania,Schmitt, Martine,Steinsoultz, Philippe,Wagner, Patrick
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p. 560 - 567
(2022/01/03)
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- Photocatalytic one-pot multidirectional N-alkylation over Pt/D-TiO2/Ti3C2: Ti3C2-based short-range directional charge transmission
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Visible-light-induced one-pot, multistep, and chemoselectivity adjustable reactions highlight the economical, sustainable, and green process. Herein, we report Pt nanoparticles dispersed on S and N co-doped titanium dioxide/titanium carbide (MXene) (3%Pt/
- Jiang, Heyan,Sheng, Meilin,Li, Yue,Kong, Shuzhen,Bian, Fengxia
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- Stable Ni catalyst encapsulated in N-doped carbon nanotubes for one-pot reductive amination of nitroarenes with aldehydes
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A novel strategy involving a popping process and carbothermal reduction was developed to create a kind of stable nickel catalyst (Ni-NC). The popping process of the mixture being composed of carbon nitride (C3N4) and nickel nitrate decomposed the nickel nitrate into nickel (oxide) nanoparticles that afterwards functioned as catalyst to grow N-containing carbon nanotubes with carbon nitride as N-containing carbon source. Finally, the nickel catalyst possessed a special structure of nanoparticles encapsulated in N-doped carbon nanotubes. This special structure is helpful to prevent nickel nanoparticles from being oxidized in air for months so that the catalyst exhibits high stability in air atmosphere. As a practical application, this encapsulated nickel catalyst exhibited excellent catalytic activity and stability in one-pot cascade reaction involving nitro-reduction and reductive amination of nitroarenes.
- Cui, Penglei,Gao, Yongjun,Liu, Yaru,Shang, Ningzhao,Wang, Chun,Xu, Yuzhu
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- Cobalt encapsulated in N?doped graphene sheet for one-pot reductive amination to synthesize secondary amines
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To develop an efficient base-metal reductive amination catalyst for synthesis of secondary amines is still a major challenge. In this study, an efficient N-doped graphene sheet-coated cobalt catalyst (Co@CN-800) was developed through a simple pyrolysis process, which could gave 99.5 % yield of N-benzylaniline by one-pot reductive amination of nitrobenzene with benzaldehyde during at least 5 cycles. Catalyst characterization and control experiments confirmed that the robust catalytic performance of the catalyst is probably due to the synergy effect of in situ generated Co-Nx encapsulated in N?doped graphene layer and appropriate meso-pore structure. Additionally, The substrate adaptability of the catalyst was proved since a variety of corresponding secondary amines were smoothly obtained under relatively mild conditions, which makes the secondary amine synthesis strategy based on Co@CN-800 shows excellent application prospect.
- Liu, Lin,Li, Wenxiu,Qi, Ran,Zhu, Qingqing,Li, Jing,Fang, Yuzhen,Kong, Xiangjin
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- A Fe single atom on N,S-doped carbon catalyst for performing N-alkylation of aromatic amines under solvent-free conditions
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A green and gram-scale strategy has been developed for the synthesis of Fe single atom/N,S-doped carbon catalyst (Fe20-SA@NSC) via the pyrolysis of polyaniline (PAN)-modified Fe,S-doped ZIFs, in which the synthesis of ZIFs can be accomplished in water at room temperature. The as-prepared catalyst exhibits superior activity in the N-alkylation of amines with alcohols via a borrowing strategy under solvent-free conditions (TOF up to 13.9 h-1). Based on the HAADF-STEM and XAFS results, Fe in this material is dispersed as the single-atom Fe1-N4S1 site. According to the experimental and theoretical calculation results, the Fe1-N4S1 site displays a better borrowing hydrogen ability than other Fe sites owing to its higher electron density. In addition, this catalyst has excellent stability and recyclability, and no obvious loss in activity is observed after 7 runs.
- Lin, Yamei,Lu, Guo-Ping,Shan, Hongbin,Wang, Pengcheng,Zhang, Kai,Zhong, Qin,Zhou, Baojing
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supporting information
p. 25128 - 25135
(2021/11/26)
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- Effect of the ancillary ligand in N-heterocyclic carbene iridium(III) catalyzed N-alkylation of amines with alcohols
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A series of air-stable N-heterocyclic carbene (NHC) Ir(III) complexes (Ir1-6), bearing various combinations of chlorine, pyridine and NHC ligands, were assayed for the N-alkylation of amines with alcohols. It was found that Ir3, with two monodentate 1,3-bis-methyl-imidazolylidene (IMe) ligands, emerged as the most active complex. A large variety of amines and primary alcohols were efficiently converted into mono-N-alkylated amines in 53–96% yields. As a special highlight, for the challenging MeOH, selective N-monomethylation could be achieved using KOH as a base under an air atmosphere. Moreover, this catalytic system was successfully applied to the gram-scale synthesis of some valuable compounds.
- Feng, Xinshu,Huang, Ming
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- Synthesis of an Fe-Pd bimetallic catalyst for: N -alkylation of amines with alcohols via a hydrogen auto-transfer methodology
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Hydrogen auto-transfer (HAT) or borrowing hydrogen (BH) methodology which combines dehydrogenation, intermediate reaction and hydrogenation, is recognized as an excellent strategy for one-pot synthesis from an economic and environmental point of view. Although much effort has been made on the development of catalysts for HAT reactions, harsh conditions, external base or large amounts of noble metals are still required in most reported catalysis systems, and thus the exploration of a highly efficient and recyclable heterogeneous catalyst remains meaningful. In this work, a novel bimetallic catalyst, Fe10Pd1/NC500 derived from bimetallic MOF NH2-MIL-101(Fe10Pd1), has been prepared, and the catalyst exhibits superior catalytic performance for the N-alkylation of amines with alcohols via a hydrogen auto-transfer methodology. High yields of the desired products were achieved at 120 °C with an alcohol/amine molar ratio of 2?:?1 and required no external additive or solvent. A distinct enhancement in catalytic performance is observed when compared with monometallic catalysts, which can be ascribed to the "synergistic effects"inside the bimetallic alloys. The N-doped carbon support has been revealed to provide the necessary basicity which avoids the requirement of an external base. Moreover, a wide substrate range and remarkable reusability have been shown by Fe10Pd1/NC500, and this work highlights new possibilities for bimetallic catalysts applied in sustainable chemistry.
- Wu, Peng-Yu,Lu, Guo-Ping,Cai, Chun
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p. 396 - 404
(2021/01/28)
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- Nickel?Copper bimetallic mesoporous nanoparticles: As an efficient heterogeneous catalyst for N-alkylation of amines with alcohols
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A bimetallic catalyst (Ni/Cu-MCM-41) is prepared via co-condensation method. The latter is characterized by Fourier transform infrared (FT-IR), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), diffuse reflectance spectroscopy (DRS), and nitrogen adsorption–desorption analysis. Catalytic performance of Ni/Cu-MCM-41 is probed in N-alkylation of amines with alcohols through a hydrogen autotransfer process. Noteworthy, this catalytic system appears very efficient for synthesis of a range of secondary and tertiary amines in good to excellent isolated yields. Moreover, the catalyst is successfully recovered and reused four times without notable decrease in its activity.
- Nasresfahani, Zahra,Kassaee, Mohamad Z.
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- Ruthenium(ii) complexes with N-heterocyclic carbene-phosphine ligands for theN-alkylation of amines with alcohols
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Metal hydride complexes are key intermediates forN-alkylation of amines with alcohols by the borrowing hydrogen/hydrogen autotransfer (BH/HA) strategy. Reactivity tuning of metal hydride complexes could adjust the dehydrogenation of alcohols and the hydrogenation of imines. Herein we report ruthenium(ii) complexes with hetero-bidentate N-heterocyclic carbene (NHC)-phosphine ligands, which realize smart pathway selection in theN-alkylated reactionviareactivity tuning of [Ru-H] species by hetero-bidentate ligands. In particular, complex6cbwith a phenyl wingtip group and BArF?counter anion, is shown to be one of the most efficient pre-catalysts for this transformation (temperature is as low as 70 °C, neat conditions and catalyst loading is as low as 0.25 mol%). A large variety of (hetero)aromatic amines and primary alcohols were efficiently converted into mono-N-alkylated amines in good to excellent isolated yields. Notably, aliphatic amines, challenging methanol and diamines could also be transformed into the desired products. Detailed control experiments and density functional theory (DFT) calculations provide insights to understand the mechanism and the smart pathway selectionvia[Ru-H] species in this process.
- Huang, Ming,Li, Yinwu,Lan, Xiao-Bing,Liu, Jiahao,Zhao, Cunyuan,Liu, Yan,Ke, Zhuofeng
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supporting information
p. 3451 - 3461
(2021/05/03)
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- Convenient and Reusable Manganese-Based Nanocatalyst for Amination of Alcohols
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The development of new sustainable nanocatalytic systems for green chemical synthesis is a growing area in chemical science. Herein, a reusable heterogeneous N-doped graphene-based manganese nanocatalyst (Mn@NrGO) for selective N-alkylation of amines with alcohols is described. Mechanistic studies illustrate that the catalytic reaction follows a domino dehydrogenation-condensation-hydrogenation sequence of alcohols and amines with the formation of water as the sole by-product. The scope of the reaction is extended to the synthesis of pharmaceutically important N-alkylated amine intermediates. The heterogeneous nature of the catalyst made it easy to separate for long-term performance, and the recycling study revealed that the catalyst was robust and retained its activity after several recycling experiments.
- Subaramanian, Murugan,Ramar, Palmurukan M.,Sivakumar, Ganesan,Kadam, Ravishankar G.,Petr, Martin,Zboril, Radek,Gawande, Manoj B.,Balaraman, Ekambaram
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p. 4334 - 4341
(2021/08/25)
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- Cooperative catalysis of molybdenum with organocatalysts for distribution of products between amines and imines
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Multi-amino groups and nitrogen donors compound was discovered as an organocatalyst for N-alkylation of alcohols with amines in the presence of Mo(CO)6. The Mo(CO)6/organocatalyst binary system has shown to be a highly active catalyst for the N-alkylation reaction between alcohols and amines with excellent tolerance of variable starting materials bearing different functional groups. Of particular note, this method possessing a superiority selectivity in the synthesis of N-alkylated amines or imines, which can be controlled by the reaction temperature. The cooperative catalysis mechanism in combination of Mo(CO)6 with organocatalyst was elucidated by control experiments.
- Wu, Di,Bu, Qingqing,Guo, Cheng,Dai, Bin,Liu, Ning
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- Switchable Imine and Amine Synthesis Catalyzed by a Well-Defined Cobalt Complex
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Switchable imine and amine synthesis catalyzed by a tripodal ligand-supported well-defined cobalt complex is presented herein. A large variety of primary alcohols and amines were selectively converted to imines or amines in good to excellent yields. It is discovered that the base plays a crucial role on the selectivity. A catalytic amount of base leads to the imine formation, while an excess loading of base results in the amine product. This strategy on product selectivity also strongly depends on the organometallic catalysts in use. We expect that the present study could provide useful insights toward selective organic synthesis and catalyst design.
- Paudel, Keshav,Xu, Shi,Hietsoi, Oleksandr,Pandey, Bedraj,Onuh, Chuka,Ding, Keying
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supporting information
p. 418 - 426
(2021/02/01)
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- Direct electrochemical reductive amination between aldehydes and amines with a H/D-donor solvent
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A novel electrochemical synthesis protocol has been achieved for reductive amination between aldehydes and amines in undivided cells at room temperature. Under metal-free and external-reductant-free electrolysis conditions, various important secondary amine products are obtained in moderate-to-high yields. Deuterium-labeling experiments have demonstrated that low-toxicity DMSO acts both as a solvent and a H-donor in the reaction. On this basis, various deuterium-labeled products with good-to-excellent D-incorporation have been synthesized by using DMSO-d6 as a solvent. Furthermore, a molecule with GR-antagonistic activity has been synthesized through further sulfonylation.
- Chen, Lu,Hong, Huanliang,Hu, Jinhui,Huang, Yubing,Li, Yibiao,Liang, Gen,Pu, Suyun,Zhu, Zhongzhi,Zou, Zirong
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supporting information
p. 5832 - 5837
(2020/11/03)
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- Zinc-Catalyzed N-Alkylation of Aromatic Amines with Alcohols: A Ligand-Free Approach
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An efficient zinc-catalyzed N-alkylation reaction of aromatic amines was achieved using aliphatic, aromatic, and heteroaromatic alcohols as the alkylating reagent. A variety of aniline derivatives, including heteroaromatic amines, underwent the N-alkylation reaction and furnished the corresponding monoalkylated products in good to excellent yields. The application of the reaction is also further demonstrated by the synthesis of a 2-phenylquinoline derivative from acetophenone and 2-aminobenzyl alcohol. Deuterium labeling experiments show that the reaction proceeds via a borrowing hydrogen process. (Figure presented.).
- Sankar, Velayudham,Kathiresan, Murugavel,Sivakumar, Bitragunta,Mannathan, Subramaniyan
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supporting information
p. 4409 - 4414
(2020/09/01)
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- Method for efficiently realizing N-alkylation reaction by using cyclic iridium catalyst
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The invention discloses a method for efficiently realizing N-alkylation reaction by using a cyclic iridium catalyst, and belongs to the technical field of pharmaceutical and chemical synthesis. The preparation method comprises the following steps of: taking amines and alcohol compounds as raw materials, a cyclic iridium complex as a catalyst and water or an organic solvent as a reaction medium, heating, stirring and reacting for 12-24 hours under the protection of inert gas, cooling to room temperature after the reaction is finished, carrying out reduced pressure distillation and concentrationto obtain a crude product, and carrying out column chromatography purification to obtain a series of amine compounds. The synthesis method of the amine compound is simple to operate, easily availablein raw materials and low in price; the method is high in reaction efficiency, good in N-alkylation selectivity, good in adaptability to various functional groups, wide in substrate universality and environmentally friendly, is carried out at the gram level, shows the potential of industrially synthesizing the N-alkylamine compound, and has wide application prospects in the fields of medicines, organic synthesis and the like.
- -
-
Paragraph 0150-0156
(2020/11/10)
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- Synthesis and characterization of N,N-chelate manganese complexes and applications in C[sbnd]N coupling reactions
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Bidentate NN-ligands have been derived from the reaction between aldehydes and 2-(aminomethyl)pyridine. The treatment of these ligands with Mn(CO)5Br gave complexes that are highly bench stable. The complexes were characterized by various analytical and spectral methods. Single-crystal XRD of complex Mn-2 was performed, which indicates an octahedral geometry around the metal center. The complexes efficiently catalyze the N-alkylation of anilines with alcohols under optimized reaction conditions.
- Das, Kuhali,Kumar, Amol,Jana, Akash,Maji, Biplab
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supporting information
(2019/12/28)
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- Mild and efficient synthesis of secondary aromatic amines by one-pot stepwise reductive amination of arylaldehydes with nitroarenes promoted by reusable nickel nanoparticles
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The one-pot stepwise reductive amination of arylaldehydes with nitroarenes is described, using reusable nickel nanoparticles (Ni-pol) as catalyst and NaBH4 as mild, inexpensive, and safe reducing agent. The proposed catalytic system holds several advantages such as the use of a non-precious and earth-abundant metal, the facile separation of the catalyst from the reaction mixture by centrifugation, excellent stability towards air and moisture, very mild reaction conditions, good recyclability, broad substrate scope with good to excellent yields, and easy scalability (up to 1.0 g). FESEM analyses indicate that the active species are cubic nanocrystals of Ni in the average cross section value of 35 nm with a quite narrow (25–45 nm) and monomodal distribution, which becomes bimodal with the recycling reactions but without agglomeration.
- Fiore, Ambra Maria,Romanazzi, Giuseppe,Dell'Anna, Maria Michela,Latronico, Mario,Leonelli, Cristina,Mali, Matilda,Rizzuti, Antonino,Mastrorilli, Piero
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- Switching the N-Alkylation of Arylamines with Benzyl Alcohols to Imine Formation Enables the One-Pot Synthesis of Enantioenriched α-N-Alkylaminophosphonates
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The selective N-alkylation of anilines with benzylic alcohols can be switched in favor of the dehydrogenative condensation process using the nitrile-ligated Kn?lker's complex by conducting the reaction either in a closed system under inert conditions, or in an open system in air. The selective formation of imines, containing reactive C=N bonds, provides an opportunity towards further functionalization. Indeed, a one-pot three-component condensation of alcohols, amines and phosphites, promoted by an iron-based Kn?lker-type complex in combination with a chiral BINOL-based phosphoric acid, provides access to enantioenriched α-N-alkylaminophosphonates.
- Hofmann, Natalie,Hultzsch, Kai C.
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supporting information
p. 3105 - 3111
(2019/06/08)
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- Catalyst-Free Reductive Coupling of Aromatic and Aliphatic Nitro Compounds with Organohalides
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A rare reductive coupling of nitro compounds with organohalides has been realized. The reaction is initiated by a partial reduction of the nitro group to a nitrenoid intermediate. Therefore, not only aromatic but also aliphatic nitro compounds are efficiently transformed into monoalkylated amines, with organohalides as the alkylating agent. Given the innate reactivity of the nitrenoid, a catalyst is not required, resulting in a high tolerance for aryl halide substituents in both starting materials.
- Rauser, Marian,Eckert, Raphael,Gerbershagen, Max,Niggemann, Meike
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supporting information
p. 6713 - 6717
(2019/04/14)
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- MOF-derived Ni?NC catalyst: Synthesis, characterization, and application in one-pot hydrogenation and reductive amination
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MOF-derived catalysts with nickel nanoparticles (NPs) uniformly embedded in nitrogen doped carbon shells were developed by pyrolysis of nickel-based metal-organic frameworks (MOFs), in which amino groups were introduced to act as the nitrogen source and possible anchoring sites for Ni NPs. The resulting materials were characterized systematically. In the architecture of the catalysts, a core-shell structure was discovered, in which Ni NPs with a diameter of 6-7 nm were surrounded by N doped graphitic layers, indicating that the introduction of amino groups into precursors is beneficial to the dispersion of NPs. One-step hydrogenation and reductive amination (OHRA) is a promising route to produce secondary amines, which avoids tedious separation of intermediates. Accordingly, we applied the prepared composites as catalysts to OHRA of benzaldehyde with nitrobenzene. Among them, the catalyst pyrolyzed at 600 °C for 1.5 h exhibited the best catalytic performance (conversion: >99%, selectivity for N-benzylaniline: 97.96%) and excellent recyclability. N-doping remarkably promotes the dispersion and stability of Ni NPs, thus improving their catalytic activity and selectivity. Furthermore, the Ni-N species as well as synergism of Ni NPs and adjacent pyridinic N may also facilitate the activation of H2. And its excellent stability and recyclability can be attributed to the core-shell structure. The achieved success in MOF-derived nanocomposites may pave the way for further industrial applications.
- Li, Jiayi,Wang, Bowei,Qin, Yutian,Tao, Qin,Chen, Ligong
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p. 3726 - 3734
(2019/07/22)
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- Alcohol Amination Catalyzed by Copper Powder as a Self-Supported Catalyst
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Catalytic alcohol amination is a sustainable reaction for N-alkyl amine synthesis. Homogeneous and supported copper catalysts have long been studied for this reaction and have given some impressive results. In this study, copper powder is found to behave as an active catalyst for alcohol amination, giving better catalytic performance than metal-oxide-supported nanocopper catalysts. Catalyst characterization suggests that the copper powder can be considered as a self-supported nanocopper catalyst (i.e., nanocopper supported on copper particles). These results might promote the study of unsupported transition metal powders in sustainable catalytic reactions.
- Wu, Yajuan,Huang, Yongji,Dai, Xingchao,Shi, Feng
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p. 3185 - 3191
(2018/11/30)
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- A Highly Active PN3 Manganese Pincer Complex Performing N-Alkylation of Amines under Mild Conditions
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A highly active Mn(I) catalyst based on a nonsymmetric PN3-ligand scaffold for the N-alkylation of amines with alcohols utilizing the borrowing hydrogen methodology is reported. A broad range of anilines and the more challenging aliphatic amines were alkylated with primary and secondary alcohols. Moreover, the combination of low catalyst loadings and mild reaction conditions provides high efficiency for this atom-economic transformation.
- Homberg, Leonard,Roller, Alexander,Hultzsch, Kai C.
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supporting information
(2019/05/07)
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- Room temperature N-heterocyclic carbene manganese catalyzed selective N-alkylation of anilines with alcohols
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The first example of room temperature non-noble metal homogeneous system catalyzed selective N-alkylation of anilines with alcohols by a bis-NHC manganese complex is presented. This system was applied to a large range of alcohols and anilines, including biologically relevant motifs and challenging methanol. Experimental and computational studies suggest an outer-sphere mechanism for this NHC-Mn system.
- Huang, Ming,Li, Yukui,Li, Yinwu,Liu, Jiahao,Shu, Siwei,Liu, Yan,Ke, Zhuofeng
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supporting information
p. 6213 - 6216
(2019/06/07)
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- Metal- and Base-Free Room-Temperature Amination of Organoboronic Acids with N-Alkyl Hydroxylamines
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We have found that readily available N-alkyl hydroxylamines are effective reagents for the amination of organoboronic acids in the presence of trichloroacetonitrile. This amination reaction proceeds rapidly at room temperature and in the absence of added metal or base, it tolerates a remarkable range of functional groups, and it can be used in the late-stage assembly of two complex units.
- Sun, Hong-Bao,Gong, Liang,Tian, Yu-Biao,Wu, Jin-Gui,Zhang, Xia,Liu, Jie,Fu, Zhengyan,Niu, Dawen
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supporting information
p. 9456 - 9460
(2018/07/29)
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- Unprecedented catalytic performance in amine syntheses: Via Pd/g-C3N4 catalyst-assisted transfer hydrogenation
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The preparation of amine compounds is very important for both the chemical industry and renewable feedstock processing. Nevertheless, difficulties remain in finding a catalytic system that is sufficiently active and environmentally benign for producing amine compounds. In this work, we report that g-C3N4 nanosheets as support materials can significantly boost the efficiency of Pd nanoparticles for the reduction of nitro compounds to primary amines. Using formic acid as a hydrogen donor and water as a solvent, the optimized 5 wt% Pd/g-C3N4 catalyst exhibited an unprecedented performance in the conversion of nitrobenzene into aniline (achieving almost full conversion with an extremely high turnover frequency of 4770 h-1 at room temperature), yielding the best activity ever reported for heterogeneously catalyzing nitro compound reduction. Pd/g-C3N4 catalyst was also active for the one-pot reductive amination of carbonyl compounds with nitro compounds to obtain the corresponding secondary amines with excellent selectivity (>90%). We proposed that the protic N-H+ and hydridic Pd-H- on Pd/g-C3N4 are the active species for the transfer hydrogenation reaction of nitro compounds. Furthermore, Pd/g-C3N4 catalyst was highly stable with a wide scope in the syntheses of various amine compounds. This work will open up a new approach for the transfer hydrogenations of nitro compounds to produce primary or secondary amines in green chemistry.
- Xu, Xingliang,Luo, Jiajun,Li, Liping,Zhang, Dan,Wang, Yan,Li, Guangshe
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supporting information
p. 2038 - 2046
(2018/05/24)
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- Manganese catalyzed N-alkylation of anilines with alcohols: Ligand enabled selectivity
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Ligand enabled Earth-abundant manganese catalyzed N-alkylation of amines with alcohols via a hydrogen auto-transfer strategy is reported. The choice of the ligand plays a significant role in the alcohol reactivity (aliphatic or aromatic) toward N-alkylation reactions.
- Landge, Vinod G.,Mondal, Akash,Kumar, Vinit,Nandakumar, Avanashiappn,Balaraman, Ekambaram
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supporting information
p. 8175 - 8180
(2018/11/23)
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- Direct access to: N -alkylated amines and imines via acceptorless dehydrogenative coupling catalyzed by a cobalt(ii)-NNN pincer complex
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A simple, phosphine-free Co(ii)-NNN pincer complex catalyzed direct N-alkylation of anilines with alcohols via hydrogen auto-transfer (HA) and selective acceptorless dehydrogenative coupling (ADC) of benzylamines with alcohols affording imines with the liberation of molecular hydrogen and water is reported.
- Midya, Siba P.,Pitchaimani, Jayaraman,Landge, Vinod G.,Madhu, Vedichi,Balaraman, Ekambaram
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p. 3469 - 3473
(2018/07/29)
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- One-pot Reductive Amination of carbonyl Compounds with Nitro Compounds by Transfer Hydrogenation over Co–Nx as catalyst
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A new method was developed for the synthesis of secondary amines through the one-pot reductive amination of carbonyl compounds with nitro compounds using formic acid as the hydrogen donor over a heterogeneous non-noble-metal catalyst (Co-Nx/C-800-AT, generated by the pyrolysis of the cobalt phthalocyanine/silica composite at 800°C under a N2 atmosphere and subsequent etching by HF). Both nitrogen and cobalt were of considerable importance in the transfer hydrogenation reactions with formic acid.
- Zhou, Peng,Zhang, Zehui
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p. 1892 - 1897
(2017/05/16)
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- One-pot reductive amination of carbonyl compounds with nitro compounds with CO/H2O as the hydrogen donor over non-noble cobalt catalyst
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The one-pot reductive amination of carbonyl compounds with nitro compounds over heterogeneous non-noble metal catalysts was developed for the first time by transfer hydrogenation with CO/H2O as the hydrogen donor. Nitrogen-doped carbon supported cobalt nanoparticles were observed to be active toward this reaction, affording structurally-diverse secondary amines with high yields. Kinetic studies revealed that the transfer hydrogenation of imines (C[dbnd]N bonds) was the rate-determining step. Reaction mechanism studies indicated that both nitrogen and cobalt nanoparticles were important for the transfer hydrogenation with CO/H2O to generate the proton (N[sbnd]H+) and hydride (Co[sbnd]H?) as the active species. Furthermore, the heterogeneous cobalt catalyst was highly stable without the loss of its catalytic activity during the recycling experiments.
- Zhou, Peng,Yu, Changlin,Jiang, Liang,Lv, Kangle,Zhang, Zehui
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p. 264 - 273
(2017/06/23)
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- General Reductive Amination of Aldehydes and Ketones with Amines and Nitroaromatics under H2 by Recyclable Iridium Catalysts
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Heterogeneous iridium catalysts were prepared and applied for the reductive amination of aldehydes and ketones with nitroaromatics and amines using H2. The iridium catalysts were prepared by pyrolysis of ionic liquid 1-methyl-3-cyanomethylimidazoulium chloride ([MCNI]Cl) with iridium chloride (IrCl3) in activated carbons. Iridium particles were well dispersed and stable in the N-doped carbon materials from [MCNI]Cl with activated carbon. The Ir@NC(600-2h) catalyst was found to be highly active and selective for the reductive amination of aldehydes and ketones using H2 and a variety of nitrobenzenes and amines were selectively converted into the corresponding secondary and tertiary amines. The Ir@NC(600-2h) catalyst can be reusable several times without evident deactivation.
- Sui, Dejun,Mao, Fei,Fan, Haipeng,Qi, Zhengliang,Huang, Jun
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supporting information
p. 1371 - 137
(2017/10/05)
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- An Efficient Homogenized Ruthenium(II) Pincer Complex for N-Monoalkylation of Amines with Alcohols
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An ionic 2,6-bis(imidazo[1,2-α]pyridin-2-yl)pyridine-based N^N^N pincer ruthenium(II) complex exhibited high efficiency in the C–N bond formation between amines and alcohols by the “borrowing hydrogen” (BH) or “hydrogen autotransfer” (HA) concept. The synthetic protocol selectively generated monoalkylated amines without formation of tertiary amines during the reaction. The unique selectivity enabled the formation of symmetrically and asymmetrically substituted diamines. This methodology features several advantages including a low catalyst loading (as low as 0.5 mol-%), a short reaction time (as short as 2 h), and excellent N-monoalkylation selectivity.
- Yang, Fa-Liu,Wang, Ying-Hui,Ni, Yong-Feng,Gao, Xiang,Song, Bing,Zhu, Xinju,Hao, Xin-Qi
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p. 3481 - 3486
(2017/07/04)
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- Cyclometalated palladium pre-catalyst for N-alkylation of amines using alcohols and regioselective alkylation of sulfanilamide using aryl alcohols
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Simple pyrazole based palladacycle-phosphine with a high turnover has been developed and applied for the N-alkylation of amines and sulfanilamide using alcohols as substrates by hydrogen borrowing strategy. N-alkylation of primary and secondary amines resulted in high isolated yields at 100–130 °C, under solvent free conditions. More challenging secondary aliphatic as well as aromatic alcohols were also successfully utilized as alkylating agents under similar reaction conditions. The turn over number reached up to 43000 for N-benzylation of aniline using benzyl alcohol. Notably, regioselective N-alkylation of 2-aminobenzothiazole and 4-aminobenzenesulfonamide to the corresponding 2-N-(alkylamino)azoles and 4-amino-(N-alkyl)benzenesulfonamides using alcohols as alkylating agents have been achieved using our new pre-catalyst-phosphine system.
- Mamidala, Ramesh,Mukundam, Vanga,Dhanunjayarao, Kunchala,Venkatasubbaiah, Krishnan
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supporting information
p. 2225 - 2233
(2017/03/24)
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- Water-Soluble Iridium N-Heterocyclic Carbene Complexes for the Alkylation of Amines with Alcohols
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A new series of water-soluble Ir complexes with N-heterocyclic carbene ligands that bear ester and amide groups has been obtained and fully characterized. The new complexes are highly reactive and selective for the alkylation of amines with alcohols with a 1:1 ratio of reactants in water and in the absence of base or other additives. The catalytic system has a broad substrate scope, which allows the synthesis of a variety of primary and secondary amines in excellent yields. A tolerance to a large range of functional groups was obtained.
- Fernandes, Ana,Royo, Beatriz
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p. 3912 - 3917
(2017/09/28)
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- A by a process for preparing amine derivatives of green method (by machine translation)
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The invention discloses a by a process for preparing amine derivatives of green method, dumping with amine compound in a non-transition metal catalyst under solvent-free conditions and through the controllable high selection dehydration alkylation reaction different amine derivatives, a non-transition metal catalyst is a halogenated hydrocarbon, halogenated hydrocarbon in an amount of 1 - 50 μM %, under the catalysis of the mellow and amine in halogenated hydrocarbon can be directly performed by the amine derivative dehydration reaction, the reaction temperature is 100 - 180 °C, the reaction time is 12 - 48 hours, the by-product is water, the reaction needs to be carried out under the protection of inert gas, simple conditions, easy to operate, the by-product is water, the reaction selectivity is controllable, the target high selectivity. Requirements for reaction condition of relatively low, primary and secondary alcohol can be used for the alkylation reagent, is suitable for the dehydration of the primary and secondary amines single alkylation reaction, is also suitable for the dehydration of the double alkylation reaction of a primary amine, with wider scope, should also has certain research and industrial application prospect. (by machine translation)
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Paragraph 0040 - 0043
(2017/08/14)
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- d-Glucose: An Efficient Reducing Agent for a Copper(II)-Mediated Arylation of Primary Amines in Water
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A copper-catalyzed Ullmann-type amination with primary amines in water with a combination of copper(II) triflate [Cu(OTf)2], dipivaloylmethane, and d-glucose is reported. The mild conditions and the use of an inexpensive catalyst as well as a renewable feedstock (d-glucose and the surfactant TPGS-750-M, which is derived from vitamin E) make this protocol a safe and convenient strategy for efficient C?N bond formation. This easy-to-handle procedure is extremely competitive compared to palladium-based reactions and may be used to synthesize N-containing molecules, such as drugs or organic light-emitting diodes (OLEDs).
- Bollenbach, Maud,Wagner, Patrick,Aquino, Pedro G. V.,Bourguignon, Jean-Jacques,Bihel, Frédéric,Salomé, Christophe,Schmitt, Martine
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p. 3244 - 3249
(2016/11/29)
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- Oxidative amination of benzylic alkanes with nitrobenzene derivatives as nitrogen sources
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The oxidative amination of inert C[sbnd]H bonds has the potential to fundamentally change chemistry but is severely limited by the low chemo- and regio-selectivity under oxidation conditions. Until now, no efficient methodology for the direct intermolecular amination of terminal sp3-C[sbnd]H bonds to N-alkyl amines has existed. Here, a new concept is proposed for the oxidative amination of the terminal sp3-C[sbnd]H bond in alkanes via the construction of a complex reaction system composed of a carbon-supported Co-Ni bimetallic catalyst, an alkane, nitrobenzene, tert-butyl hydroperoxide and hydrogen. This system allows the reduction of nitrobenzene to aniline and the further oxidative amination of the alkane. Nitrobenzene and toluene derivatives can be successfully transformed into the corresponding N-benzyl aniline derivatives with up to 95% isolated yields, and the reaction shows excellent functional group tolerance. This approach offers a new concept for catalyst design and may strongly promote the study of inert C[sbnd]H bond activation and the synthesis of functional N-containing compounds.
- Pang, Shaofeng,Shi, Feng
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supporting information
p. 5872 - 5876
(2016/12/07)
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- A quick Chan-Lam C-N and C-S cross coupling at room temperature in the presence of square pyramidal [Cu(DMAP)4I]I as a catalyst
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A rapid and efficient protocol for C-N and C-S cross coupling has been developed using a new square pyramidal copper complex, [Cu(DMAP)4I]I. The complex was successfully synthesized via a disproportionation reaction of CuI and DMAP in DMSO. The catalytic activity of the complex was found to be excellent for Chan-Lam coupling reaction between aryl boronic acid and amine, amide, azide or thiol. The reaction could be carried out in the presence of only 2 mol% of the copper catalyst in methanol at room temperature within a short time.
- Roy, Subhasish,Sarma, Manas Jyoti,Kashyap, Bishwapran,Phukan, Prodeep
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supporting information
p. 1170 - 1173
(2016/01/15)
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- Direct reductive amination of aldehydes with nitroarenes using bio-renewable formic acid as a hydrogen source
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Reductive amination (RA) is one of the most important transformations in organic chemistry. A versatile and sustainable gas-free RA of aldehydes carried out directly with cheaply available nitroarenes using stoichiometric amounts of non-toxic and entirely renewable formic acid (FA) as the terminal reductant is described herein. A single phase rutile titania supported gold (Au/TiO2-R) catalyst is shown to catalyse efficiently this FA-based direct RA in neat water under mild reaction conditions. The broad scope, mild and neutral conditions, together with CO2 and water as environmental harmless byproducts, make this transformation very useful. Moreover, straightforward examples of the direct construction of bioactive heterocyclic compounds containing a benzimidazole motif were achieved through this protocol.
- Zhang, Qi,Li, Shu-Shuang,Zhu, Ming-Ming,Liu, Yong-Mei,He, He-Yong,Cao, Yong
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supporting information
p. 2507 - 2513
(2016/05/19)
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- Heterogeneous cobalt catalysts for reductive amination with H2: General synthesis of secondary and tertiary amines
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Heterogeneous Co@NC catalysts were prepared, characterized and applied for the reductive amination of aldehydes and ketones with H2 gas. The Co catalyst Co@NC (800-2 h) was found to be active and selective for the reductive amination of aldehydes and ketones using H2 gas. Thus, general synthesis of secondary and tertiary amines was developed by the Co-catalyzed reductive amination with H2 gas, and various secondary and tertiary amines can be obtained in high yields. Moreover, a practical synthesis of N-substituted isoindolinones was also presented by a one step process with the Co@NC (800-2 h) catalyst. The Co@NC (800-2 h) catalyst is reusable at least five times without evident loss of activity.
- Mao, Fei,Sui, Dejun,Qi, Zhengliang,Fan, Haipeng,Chen, Rizhi,Huang, Jun
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p. 94068 - 94073
(2016/10/22)
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- Magnetic nanoparticle-supported phosphine gold(i) complex: A highly efficient and recyclable catalyst for the direct reductive amination of aldehydes and ketones
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The direct reductive amination of aldehydes and ketones has been achieved in dichloromethane at room temperature by using a magnetic nanoparticle-supported phosphine gold(i) complex [Fe3O4@SiO2-P-AuCl] as the catalyst and ethyl Hantzsch ester as the hydrogen source, yielding a variety of secondary amines in excellent yields under neutral conditions. The new heterogeneous gold catalyst can be prepared by a simple procedure from commercially readily available reagents and can easily be separated from the reaction mixture by applying an external magnet and recycled at least 10 times without any loss of activity.
- Yang, Weisen,Wei, Li,Yi, Feiyan,Cai, Mingzhong
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p. 4554 - 4564
(2016/07/06)
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- Copper-catalyzed radical reactions of 2-azido-N-arylacrylamides with 1-(trifluoromethyl)-1,2-benziodoxole and 1-azidyl-1,2-benziodoxole
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The reactions of 2-azido-N-arylacrylamides with trifluoromethyl radicals and azidyl radicals were investigated by using Togni's reagent and Zhdankin's reagent as the source of these radicals. Under the catalysis of CuI, Togni's reagent was firstly converted into the trifluoromethyl radical, which then reacted with 2-azido-N-arylacrylamides to afford the corresponding α-(arylaminocarbonyl)iminyl radicals. The cyclization of the iminyl radicals delivered quinoxalin-2(1H)-one products in moderate yields. A similar reaction took place between 2-azido-N-arylacrylamides and the azidyl radical. In the latter cases, the reaction produced 3-azidomethyl and 3-cyano-subsituted quinoxalin-2(1H)-ones. This study not only helps elucidate the factors influencing the cyclization of α-(arylaminocarbonyl)iminyl radicals, but also provides a new approach towards quinoxalin-2-ones.
- Yang, Tonghao,Zhu, Haizhen,Yu, Wei
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supporting information
p. 3376 - 3384
(2016/04/09)
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- Carbon dioxide promoted reductive amination of aldehydes in water mediated by iron powder and catalytic palladium on activated carbon
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A mixture of iron powder and catalytic palladium on activated carbon has been developed for reductive amination of various aromatic aldehydes, including 2-pyridinecarboxaldehyde, in water under CO2 atmosphere. The reversible reaction of CO2 with water could form carbonic acid and hydrogen transfer from water to Pd(0) took place with the presence of iron powder, leading to formation of high-active Pd hydrides for the reductive amination process. On the other hand, the reaction system could be inherently neutralized by ready removal of CO2, thus resulting in facile post-processing.
- Ma, Ran,Zhou, Yue-Biao,He, Liang-Nian
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- Scalable synthesis of secondary and tertiary amines by heterogeneous Pt-Sn/γ-Al2O3catalyzed N-alkylation of amines with alcohols
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Synthesis of secondary and tertiary amines has been efficiently realized from the N-alkylation of amines with alcohols by means of heterogeneous bimetallic Pt-Sn/γ-Al2O3catalyst (0.5?wt % Pt, molar ratio Pt:Sn?=?1:3) through a borrowing hydrogen strategy. The Pt-Sn/γ-Al2O3catalyst has exhibited very high catalytic activity towards a wide range of amines and alcohols, and can be conveniently recycled without Pt metal leaching. The present protocol was applied for the synthesis of N-phenylbenzylamine in 96% isolated yield from aniline and benzyl alcohol on a 2.1?kg scale of the substrates, demonstrating its potential applicability for higher-order amine synthesis.
- Wu, Kaikai,He, Wei,Sun, Chenglin,Yu, Zhengkun
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supporting information
p. 8516 - 8521
(2016/11/28)
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- Selective catalytic Hofmann: N -alkylation of poor nucleophilic amines and amides with catalytic amounts of alkyl halides
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Using only catalytic amounts of alkyl halides in the reactions of poor nucleophilic amines/amides and alcohols led to a selective Hofmann N-alkylation reaction catalytic in alkyl halides, providing a practical and efficient method for the practical synthesis of mono- or di-alkylated amines/amides in high selectivities. This new method avoids the use of large amounts of bases, alkyl halides, and solvents, and generates water as the only byproduct. Preliminary mechanistic studies showed that alkyl halides are key intermediates/catalysts regeneratable in the reaction cycle.
- Xu, Qing,Xie, Huamei,Zhang, Er-Lei,Ma, Xiantao,Chen, Jianhui,Yu, Xiao-Chun,Li, Huan
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supporting information
p. 3940 - 3944
(2016/07/21)
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- Method of producing higher amine (by machine translation)
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PROBLEM TO BE SOLVED: To provide a method of producing a secondary or tertiary higher amine. SOLUTION: The method of producing a higher amine comprises allowing a primary or secondary amine to react with an alcohol in the presence of at least one species of hydrogen halide selected from hydrogen chloride, hydrogen bromide and hydrogen iodide, or in the presence of a compound capable of producing a hydrogen halide (such as 1,3,5-triazo-2,4,6-triphosphorine-2,2,4,4,6,6-chloride). If the raw material amine is a primary amine, a secondary higher amine and a tertiary higher amine can be produced. If the raw material amine is a secondary amine, a tertiary higher amine can be produced. COPYRIGHT: (C)2012,JPO&INPIT
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Paragraph 0048; 0063
(2016/10/08)
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- Indium-catalyzed reduction of secondary amides with a hydrosiloxane leading to secondary amines
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Described herein is that the selective reduction of aromatic/aliphatic secondary amides using a combination of InI3 and TMDS (1,1,3,3-tetramethyldisiloxane), which led to the production of the corresponding secondary amines. This reducing system showed a relatively high tolerance to a variety of functional groups, such as an alkyl, an alkoxy, a halogen, a cyano, an ether, a thioether, a heterocyclic ring, and a terminal alkene group.
- Sakai, Norio,Takeoka, Masashi,Kumaki, Takayuki,Asano, Hirotaka,Konakahara, Takeo,Ogiwara, Yohei
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supporting information
p. 6448 - 6451
(2015/11/16)
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- An Air-Stable Nickel(0) Phosphite Precatalyst for Primary Alkylamine C-N Cross-Coupling Reactions
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In this report we describe the design and preparation of a new air-stable nickel phosphite based catalyst for unique C-N bond forming processes. Specifically, (BINAP)Ni[P(OPh)3]2, is presented as an effective catalyst for a range of amination reactions between aryl halides and primary alkylamines. The results are supported by relevant kinetic studies, DFT calculations and a catalytic cycle indicating possible reaction intermediates. The amination reaction between a series of aryl halides and primary alkylamines is described using a new air-stable nickel phosphite based catalyst (BINAP)Ni[P(OPh)3]2.
- Kampmann, Sven S.,Skelton, Brian W.,Wild, Duncan A.,Koutsantonis, George A.,Stewart, Scott G.
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supporting information
p. 5995 - 6004
(2015/09/22)
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- Tert-Butyl Hydroperoxide and Tetrabutylammonium Iodide-Promoted Free Radical Cyclization of α-Imino-N-arylamides and α-Azido-N-arylamides
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The oxidizing system of tert-butyl hydroperoxide (TBHP) and tetrabutylammonium iodide (TBAI) is capable of generating α-(arylaminocarbonyl)iminyl radicals from ethyl 2-(N-arylcarbamoyl)-2-iminoacetates. These iminyl radicals preferably undergo intramolecular ipso attack on the benzene ring to give azaspirocyclohexadienyl radicals, which are readily captured by molecular oxygen under an oxygen atmosphere to yield azaspirocyclohexadienones. In the absence of oxygen, the reaction affords quinoxalin-2-one products. This oxidizing system is also effective to convert α-aryl-α-azido-N-arylamides to the corresponding iminyl radicals under basic conditions (sodium tert-butoxide, t-BuONa), and the subsequent cyclization of these iminyl radicals results in the formation of azaspirocyclohexadienone products in high yields under an oxygen atmosphere. Plausible mechanisms are proposed to rationalize the experimental results, and factors influencing the reactions are discussed.
- Li, Dianjun,Yang, Tonghao,Su, Hailin,Yu, Wei
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supporting information
p. 2529 - 2539
(2015/08/18)
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- Alkylation of Amines with Alcohols and Amines by a Single Catalyst under Mild Conditions
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An efficient catalytic system for the alkylation of amines with either alcohols or amines under mild conditions has been developed, using cyclometallated iridium complexes as catalysts. The method has broad substrate scope, allowing for the synthesis of a diverse range of secondary and tertiary amines with good to excellent yields. By controlling the ratio of substrates, both mono- and bis-alkylated amines can be obtained with high selectivity. In particular, methanol can be used as the alkylating reagent, affording N-methylated products selectively. A strong solvent effect is observed for the reaction.
- Zou, Qingzhu,Wang, Chao,Smith, Jen,Xue, Dong,Xiao, Jianliang
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supporting information
p. 9656 - 9661
(2015/06/30)
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