- Selective C-C bonds formation, N-alkylation and benzo[d]imidazoles synthesis by a recyclable zinc composite
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Earth abundant metals are much less expensive, promising, valuable metals and could be served as catalysts for the borrowing hydrogen reaction, dehydrogenation and heterocycles synthesis, instead of noble metals. The uniformly dispersed zinc composites were designed, synthesized and carefully characterized by means of XPS, EDS, TEM and XRD. The resulting zinc composite showed good catalytic activity for the N-alkylation of amines with amines, ketones with alcohols in water under base-free conditions, while unsaturated carbonyl compounds could also be synthesized by tuning the reaction conditions. Importantly, it was the first time to realize the synthesis of 2-aryl-1H-benzo[d]imidazole derivatives by using this zinc composite under green conditions. Meanwhile, this zinc catalyst could be easily recovered and reused for at least five times.
- Zhu, Guanxin,Duan, Zheng-Chao,Zhu, Haiyan,Ye, Dongdong,Wang, Dawei
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supporting information
p. 266 - 270
(2021/08/06)
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- COLORANT DISPERSION LIQUID AND PRINTING METHOD OF HYDROPHOBIC FIBER
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PROBLEM TO BE SOLVED: To provide black dispersion liquid for inkjet printing ink that can manufacture a dyed thing excellent in color rendering, can obtain high quality dyed thing that can obtain high concentration dyed thing, and has excellent redispersion. SOLUTION: A colorant dispersion comprises (A) a compound expressed by a formula (1), and (B) polyoxyethylene arylphenyl ether-based dispersant and polyoxyethylene arylphenyl ether sulfate-based dispersant. (R1 is H or a nitro group; R2 and R3 are independently C1 to C4 alkoxy group or C1 to C4 alkyl group that may be substituted with a phenyl group; R4 is halogen atom; and R2 and R3 may be mutually coupled to form a ring.) SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
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Paragraph 0100; 0102-0103
(2021/08/13)
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- COLORED DISPERSION, INK COMPOSITION USING THE SAME, AND DISPERSION STABILITY IMPROVEMENT METHOD THEREWITH AND PRINTING METHOD OF HYDROPHOBIC FIBER
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PROBLEM TO BE SOLVED: To provide dispersion liquid for inkjet printing ink that can manufacture a dyed thing excellent in color rendering, can obtain the dyeing having high sublimation transfer efficiency, high concentration and high quality, in sublimation transfer dying using inkjet printing, furthermore, excellent in storage stability. SOLUTION: A colorant dispersion comprises (A) a compound expressed by a formula (1), (B) C.I. Disperse Blue 360, and (C) a dispersant, in which when a total content of (A) and (B) is set to 100, a content of (B) is 10 or larger and 90 or smaller, (C) the dispersant contains at least any one selected from the group consisting of polyoxyethylene aryl phenyl ether-based dispersant, and polyoxyethylene arylphenyl ether sulfate-based dispersant. (R1 is H or a nitro group; R2 and R3 may be independently substituted with C1-C4 alkoxy group or C1-C4 alkyl groups that may be substituted with phenyl group; R4 is halogen atom; and R2 and R3 may be mutually coupling to form a ring.) SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
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-
Paragraph 0103; 0105-0106
(2021/08/13)
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- Silver/manganese dioxide nanorod catalyzed hydrogen-borrowing reactions and tert-butyl ester synthesis
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Silver/manganese dioxide (Ag@MnO2) nanorods are synthesized and characterized by scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray powder diffraction, and X-ray photoelectron spectroscopy. It was discovered that Ag@MnO2 nanorods can realize hydrogen-borrowing reactions in high yields and are also effective for the synthesis of tert-butyl esters from aryl cyanides and tert-butyl hydroperoxide in a short period of time. Mechanistic experiments revealed that this catalytic system acts as a Lewis acid in hydrogen-borrowing reactions, while the synthesis of tert-butyl esters occurs through a radical pathway. This is the first report on the excellent catalytic activity of Ag@MnO2 nanorods as a catalyst.
- Luo, Huanhuan,Wang, Dawei,Xu, Zhaojun,Yang, Bobin,Yang, Yike
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p. 708 - 715
(2021/03/03)
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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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- The synthesis and structure of an amazing and stable carbonized material Cu-PC@OFM and its catalytic applications in water with mechanism explorations
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An amazing and stable carbonized octahedral frame material Cu-PC@OFM was synthesized and characterized through HRTEM, SEM, XRD, XPS, and Raman spectroscopy and nitrogen adsorption/desorption analysis. In particular, the carbon matrix carrier loaded with nano-copper not only maintains the original structure, but also the nano copper particles generatedin situsignificantly improve the catalytic performance and stability. It was disclosed that the copper-based catalyst material Cu-PC@OFM showed high catalytic activity in the borrowing hydrogen reaction and the synthesis of 1-benzyl-2-aryl-1H-benzo[d]imidazole derivatives with high yields in water. This copper catalytic system provided a much greener and efficient catalyst for the synthesis of functionalized amines and 1-benzyl-2-aryl-1H-benzo[d]imidazoles with good recovery performance in water, which was the first example for the Cu-PC@OFM material-catalyzed synthesis of 1-benzyl-2-aryl-1H-benzo[d]imidazoles. In addition, a plausible reaction mechanism was proposed through some condition control experiments, deuterium labeling experiments and separation of intermediates experiments.
- Tian, An-Qi,Luo, Xiang-Hao,Ren, Zhi-Lin,Zhao, Jun,Wang, Long
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supporting information
p. 9614 - 9620
(2021/06/12)
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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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- Biorenewable carbon-supported Ru catalyst for: N -alkylation of amines with alcohols and selective hydrogenation of nitroarenes
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Herein, we developed a renewable carbon-supported Ru catalyst (Ru/PNC-700), which was facilely prepared via simple impregnation followed by the pyrolysis process. The prepared Ru/PNC-700 catalyst demonstrated remarkable catalytic activity in terms of conversion and selectivity towards N-alkylation of anilines with benzyl alcohol and chemoselective hydrogenation of aromatic nitro compounds. In addition, local anesthetic pharmaceutical agents (e.g., butamben and benzocaine), including key drug intermediates, were synthesized in excellent yields under mild conditions and in the presence of water as a green solvent. Moreover, the prepared Ru/PNC-700 catalyst could be easily recovered and reused up to five times without any apparent loss in activity and selectivity.
- Goyal, Vishakha,Narani, Anand,Natte, Kishore,Poddar, Mukesh Kumar,Ray, Anjan,Sarki, Naina,Tripathi, Deependra
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p. 14687 - 14694
(2021/08/23)
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- [(PPh3)2NiCl2]-Catalyzed C-N bond formation reaction via borrowing hydrogen strategy: Access to diverse secondary amines and quinolines
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Commercially available [(PPh3)2NiCl2] was found to be an efficient catalyst for the mono-N-alkylation of (hetero)- A romatic amines, employing alcohols to deliver diverse secondary amines, including the drug intermediates chloropyramine (5b) and mepyramine (5c), in excellent yields (up to 97%) via the borrowing hydrogen strategy. This method shows a superior activity (TON up to 10000) with a broad substrate scope at a low catalyst loading of 1 mol % and a short reaction time. Further, this strategy is also successful in accessing various quinoline derivatives following the acceptorless dehydrogenation pathway.
- Donthireddy,Pandey, Vipin K.,Rit, Arnab
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p. 6994 - 7001
(2021/06/09)
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- BF3·Et2O as a metal-free catalyst for direct reductive amination of aldehydes with amines using formic acid as a reductant
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A versatile metal- and base-free direct reductive amination of aldehydes with amines using formic acid as a reductant under the catalysis of inexpensive BF3·Et2O has been developed. A wide range of primary and secondary amines and diversely substituted aldehydes are compatible with this transformation, allowing facile access to various secondary and tertiary amines in high yields with wide functional group tolerance. Moreover, the method is convenient for the late-stage functionalization of bioactive compounds and preparation of commercialized drug molecules and biologically relevant N-heterocycles. The procedure has the advantages of simple operation and workup and easy scale-up, and does not require dry conditions, an inert atmosphere or a water scavenger. Mechanistic studies reveal the involvement of imine activation by BF3and hydride transfer from formic acid.
- Fan, Qing-Hua,Liu, Xintong,Luo, Zhenli,Pan, Yixiao,Xu, Lijin,Yang, Ji,Yao, Zhen,Zhang, Xin
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supporting information
p. 5205 - 5211
(2021/07/29)
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- Iron-Catalyzed Oxidative Amination of Benzylic C(sp3)–H Bonds with Anilines
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Iron-catalyzed oxidative amination of benzylic C(sp3)–H bonds with anilines bearing electron-withdrawing groups (EWGs) or electron-donating groups (EDGs) is realized based on simple variations of N-substituents on imidazolium cations in novel ionic Fe(III) complexes. The structural modification of the imidazolium cation resulted in regulation of the redox potential and the catalytic performance of the iron metal center. Using DTBP as oxidant, [HItBu][FeBr4] showed the highest catalytic activity for anilines bearing EWGs, while [HIPym][FeBr4] was more efficient for EDG-substituted anilines. This work provides alternative access to benzylamines with the advantages of both a wide substrate scope and iron catalysis.
- Song, Yan-Ling,Li, Bei,Xie, Zhen-Biao,Wang, Dan,Sun, Hong-Mei
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p. 17975 - 17985
(2021/12/13)
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- Ultrasound-assisted rapid reduction of nitroaromatics to anilines using gallium metal
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The reduction of nitroaromatic compounds to anilines is widely used throughout organic synthesis. Typical methods of performing this transformation utilize hydrogenation over a pyrophoric catalyst or a finely divided reducing metal, which often affords heterogeneous mixtures that are difficult to purify. Herein, we report for the first time the use of gallium metal as a reducing agent in organic synthesis. The reaction proceeds under aerobic conditions and affords homogeneous mixtures for a convenient workup. Using this method, twelve anilines were obtained in 33% to quantitative yields with short reaction times of 10-60 minutes.
- Bento, Ian,Bernaldez, Mabel,Noguchi, Ryden,Kawakami, Joel
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supporting information
p. 1404 - 1407
(2020/03/31)
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- Pyridine mediated transition-metal-free direct alkylation of anilines using alcohols: via borrowing hydrogen conditions
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Herein, we report pyridine and other similar azaaromatics as efficient biomimetic hydrogen shuttles for a transition-metal-free direct N-alkylation of aryl and heteroaryl amines using a variety of benzylic and straight chain alcohols. Mechanistic studies including deuterium labeling and the isolation of dihydro-intermediates of the benzannulated pyridine confirmed the role of pyridine and a borrowing hydrogen process operating in these reactions. In addition, we have extended this methodology for the development of dehydrogenative synthesis of quinolines and indoles, as well as the transfer hydrogenation of ketones. This journal is
- Pothikumar, Rajagopal,Bhat, Venugopal T,Namitharan, Kayambu
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supporting information
p. 13607 - 13610
(2020/11/17)
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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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- Visible-light-enabled regioselective aerobic oxidative C(sp2)-H thiocyanation of aromatic compounds by Eosin-Y photocatalyst
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Herein, visible-light-enabled regioselective aerobic oxidative C(sp2)-H thiocyanation of aromatic compounds has been developed by employing eosin-Y as effective photocatalyst and oxygen as the green terminal oxidant. This process featured green, efficient and operationally simple. Furthermore, the practicality and utility of this protocol was demonstrated by the gram scale synthesis. Mechanistic studies suggested that this reaction was realized via a photoredox radical pathway.
- Yi, Bing,Wen, Xiaoyong,Yi, Ziqi,Xie, Yanjun,Wang, Qiang,Tan, Jian-Ping
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supporting information
(2020/11/19)
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- Efficient One-Pot Reductive Aminations of Carbonyl Compounds with Aquivion-Fe as a Recyclable Catalyst and Sodium Borohydride
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A one-pot reductive amination of aldehydes and ketones with NaBH4 was developed with a view to providing efficient, economical and greener synthetic conditions. A recyclable iron-based Lewis catalyst, Aquivion-Fe, was used to promote imine formation in cyclopentyl methyl ether, followed by the addition of a small amount of methanol to the reaction mixture to enable C=N reduction by NaBH4. The protocol, applied to a wide number of amines and carbonyl compounds, resulted in ever complete conversion of these latter with excellent chemoselectivity towards the expected amination products in the most cases. Isolated yields, determined for a selection of the screened substrates, were found consistent with the previously obtained conversion and selectivity data. Cinacalcet, an important active pharmaceutical ingredient, was efficiently prepared by the title procedure.
- Airoldi, Veronica,Piccolo, Oreste,Roda, Gabriella,Appiani, Rebecca,Bavo, Francesco,Tassini, Riccardo,Paganelli, Stefano,Arnoldi, Sebastiano,Pallavicini, Marco,Bolchi, Cristiano
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supporting information
p. 162 - 168
(2019/12/11)
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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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- Unsymmetrical triazolyl-naphthyridinyl-pyridine bridged highly active copper complexes supported on reduced graphene oxide and their application in water
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A novel unsymmetrical triazolyl-naphthyridinyl-pyridine ligand was designed and synthesized, and employed in the synthesis of a heterogeneous copper complex on reduced graphene oxide. The resulting copper composite was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDX). This supported copper catalyst containing unsymmetrical triazolyl-naphthyridinyl-pyridine (only 0.1 mol%) showed excellent catalytic activity in water with good recyclability. Various functionalized quinoline derivatives were successfully synthesized in high yields through the green strategy in water. Other heterocyclic compounds, such as pyridine, 2-(pyridin-2-yl)quinoline, 1,8-naphthyridine, 5,6-dihydronaphtho[1,2-b][1,8]naphthyridine and 2-(pyridin-2-yl)-1,8-naphthyridine derivatives, were achieved in water with more than 80% yields. Mechanism studies revealed that this transformation occurs via dehydrogenation, condensation, and transfer hydrogenation and dehydrogenation processes which was supported by a deuterium labeling experiment.
- Hu, Wenkang,Zhang, Yilin,Zhu, Haiyan,Ye, Dongdong,Wang, Dawei
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supporting information
p. 5345 - 5351
(2019/10/11)
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- A microwave-assisted SmI2-catalyzed direct N-alkylation of anilines with alcohols
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A new protocol for the alkylation of aromatic amines has been described using alcohols in the presence of SmI2 as a catalyst with the generation of water as the sole byproduct. The reaction proceeds under MW conditions and selectively generates monoalkylated amines. This protocol features a broad substrate scope and good functional-group tolerance with moderate to high yields.
- Gour, Jitendra,Gatadi, Srikanth,Malasala, Satyaveni,Yaddanpudi, Madhavi Venkata,Nanduri, Srinivas
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p. 7488 - 7494
(2019/06/14)
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- Self-Suspended Nanoparticles for N-Alkylation Reactions: A New Concept for Catalysis
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The catalytic activity of snowman-like and core-shell Fe3O4/Au nanoparticles (NPs), obtained through a “wet chemistry” approach which directly restitutes nanocatalysts stable and highly active in the reaction medium, was tested towards N-alkylation reactions. The nanocatalysts were tested for the synthesis of secondary amines. The core-shell NPs, thanks to the surface properties, homogeneous dispersion and intimate connection with reagents in the catalyst medium, exhibited an excellent catalytic activity (e. g. >99 % yield and conversion of aniline in very short time and mild conditions). Owing to the magnetic part, the nanoparticles can be easily separated and reused, showing an almost stable activity after 10 cycles.
- Sarno, Maria,Cirillo, Claudia,Iuliano, Mariagrazia
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- Unsymmetrical indazolyl-pyridinyl-triazole ligand-promoted highly active iridium complexes supported on hydrotalcite and its catalytic application in water
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Herein, an indazolyl-pyridinyl-triazole ligand was synthesized and its iridium complex supported on hydrotalcite was characterized via X-ray power diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray (EDX) spectroscopy and transmission electron microscopy (TEM). This new heterogeneous catalyst bearing the unsymmetrical indazolyl-pyridinyl-triazole ligand exhibits high catalytic activity in water. Both functionalized amines and imines were obtained from the challenging selective reaction of benzylamines with arylamines through transfer hydrogenation and dehydrogenation under clean conditions. In particular, it was observed that this catalyst system showed good recovery performance in water. Mechanistic studies showed that this transformation occurs via amine dehydrogenation, hydrolysis and condensation processes. The direct capture of the reaction intermediate provides sufficient proof for this process.
- Ge, Chenyang,Sang, Xinxin,Yao, Wei,Zhang, Liang,Wang, Dawei
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supporting information
p. 1805 - 1812
(2018/04/30)
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- N-Alkylation of Aniline and Its Derivatives by Alcohols in the Presence of Copper Compounds
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N-Alkyl- and N,N-dialkyl-substituted anilines were obtained in the reaction of aniline and its derivatives with primary and secondary alcohols in the presence of catalysts CuCl2·2H2O, CuBr2 and halomethanes as promoters.
- Bayguzina,Musina, Ch. F.,Khusnutdinov
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p. 1652 - 1659
(2019/02/12)
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- Method for synthesizing N-alkyl arylamine
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The invention discloses a method for synthesizing N-alkyl arylamine. The method comprises the steps of adding amine, alcohol, a metal iridium catalyst, alkali to a reaction vessel for reflux reaction,cooling to room temperature after reaction, spin-drying a solvent and then conducting separation on columns to obtain a target compound. According to the method for synthesizing the N-alkyl arylamine, a series of N-benzylaniline derivatives are prepared by using transition metal iridium as the catalyst, weak base is used, by-product is water, and a product has relatively good yield, and has certain applicable value.
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-
Paragraph 0065-0067
(2018/03/24)
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- Ruthenium(II)-NNN-Pincer-Complex-Catalyzed Reactions Between Various Alcohols and Amines for Sustainable C?N and C?C Bond Formation
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An air and moisture stable 2-hydroxypyridine based bifunctional ruthenium NNN-pincer complex catalyzed efficient (TON=42840) N-alkylation of amines under mild conditions. Surprisingly, with cyclic secondary amines this methodology selectively produced only amides. Notably, N-methylation of several amines was achieved by using methanol as a green methylating agent. Furthermore, with lower catalyst loading (0.2 mol%) and shorter reaction time (6 h) numerous substituted quinolines were synthesized from 2-aminobenzyl alcohols and secondary alcohols. The effectiveness of this protocol was further extended by successfully synthesizing 2-alkylaminoquinolines in a one-pot fashion from amino alcohol, aliphatic nitriles, and alcohols. Gram scale synthesis of various compounds was also investigated to demonstrate the synthetic applicability of this methodology. (Figure presented.).
- Maji, Milan,Chakrabarti, Kaushik,Paul, Bhaskar,Roy, Bivas Chandra,Kundu, Sabuj
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supporting information
p. 722 - 729
(2018/01/01)
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- BINAP-copper supported by hydrotalcite as an efficient catalyst for the borrowing hydrogen reaction and dehydrogenation cyclization under water or solvent-free conditions
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A BINAP-Cu system supported by hydrotalcite has been developed and proved to be a highly efficient catalyst for the atom-efficient and green borrowing hydrogen reaction and dehydrogenative cyclization. This BINAP-Cu complex supported by hydrotalcite is highly air-stable and can be recycled at least five times under solvent-free conditions. Notably, 1-benzyl-2-aryl-1H-benzo[d]imidazole derivatives could be synthesized from alcohols in only one step with water as the solvent for the first time. This provided a much greener and efficient catalytic method towards the synthesis of functionalized amines, ketones and 1-benzyl-2-aryl-1H-benzo[d]imidazole derivatives with high yields under water or solvent-free conditions.
- Xu, Zhaojun,Yu, Xiaoli,Sang, Xinxin,Wang, Dawei
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supporting information
p. 2571 - 2577
(2018/06/11)
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- Molecular docking, 3D-QSAR, molecular dynamics, synthesis and anticancer activity of tyrosine kinase 2 (TYK 2) inhibitors
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A therapeutic rationale is proposed by selectively targeting tyrosine kinase 2 (TYK 2) to obtain potent TYK 2 inhibitors by molecular modeling studies. In the present study, we have taken tyrosine kinase (TYK 2) inhibitors and carried out molecular docking, 3 D quantitative structure–activity relationship (3D-QSAR) analysis and molecular dynamics (MD). Based on the 3D-QSAR results thirteen new compounds (R-1 to R-13) were designed and synthesized in good yields. The synthesized molecules were evaluated for their in vitro anticancer activity against LnCap and A549 cell lines. The molecules R-1, R-3, R-5, R-7, and R-10 exhibited considerable anti cancer activity.
- Itteboina, Ramesh,Ballu, Srilata,Sivan, Sree Kanth,Manga, Vijjulatha
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p. 462 - 474
(2019/05/08)
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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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- Use of a Cyclometalated Iridium(III) Complex Containing a N∧C∧N-Coordinating Terdentate Ligand as a Catalyst for the α-Alkylation of Ketones and N-Alkylation of Amines with Alcohols
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A cyclometalated iridium(III) complex containing a N∧C∧N-coordinating terdentate ligand [Ir(dpyx-N,C,N)Cl(μ-Cl)]2 was found to be a general and highly effective catalyst for the α-alkylation of ketones and N-alkylation of amines with alcohols. In the presence of catalyst (1 mol % Ir) and base (0.2-0.5 equiv), a variety of desirable products were obtained in good yields under an air atmosphere. Notably, this research exhibited the new potential of Ir(III) complexes bearing non-Cp? ligand and will facilitate the progress of the hydrogen autotransfer process.
- Liu, Pengcheng,Liang, Ran,Lu, Lei,Yu, Zhentao,Li, Feng
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p. 1943 - 1950
(2017/02/26)
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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 0052 - 0055
(2017/08/14)
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- A Simple Cobalt(II) Chloride Catalyzed N -Alkylation of Amines with Alcohols
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A facile cobalt-catalyzed N -alkylation of amines with alcohols using inexpensive, commercially available CoCl 2 ·6H 2 O is reported. Employing this readily available cobalt catalyst, a variety of amines with wide functional group tolerance were selectively alkylated under benign conditions.
- Midya, Siba P.,Mondal, Akash,Begum, Ayesha,Balaraman, Ekambaram
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supporting information
p. 3957 - 3961
(2017/08/29)
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- Tunable Triazole-Phosphine-Copper Catalysts for the Synthesis of 2-Aryl-1H-benzo[d]imidazoles from Benzyl Alcohols and Diamines by Acceptorless Dehydrogenation and Borrowing Hydrogen Reactions
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Triazole-phosphine-copper complexes (TAP?Cu) have been synthesized and applied as tunable and efficient catalysts for the selective synthesis of fluoro-substituted 2-aryl-1H-benzo[d]imidazole and 1-benzyl-2-aryl-1H-benzo[d]imidazole derivatives from simple alcohols in only one step. TAP?Cu exhibited excellent and tunable catalytic activity for both dehydrogenation and borrowing hydrogen reactions with more than 80 examples being demonstrated for the first time. It was observed that the ligand played a critical role in catalyst activity. Mechanistic studies and deuterium labeling experiments indicated that the reactions proceeded by an initial and reversible alcohol dehydrogenation resulting in a copper hydride intermediate. This was also supported by the direct observation of a diagnostic copper hydride signal by solid-state infrared spectroscopy. The TAP?Cu-H complex showed absorptions at 912 cm?1 that could be assigned to copper?hydride stretches. Furthermore, the direct trapping of an intermediate bisimine was also successfully performed. (Figure presented.).
- Xu, Zhaojun,Wang, Duo-Sheng,Yu, Xiaoli,Yang, Yongchun,Wang, Dawei
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supporting information
p. 3332 - 3340
(2017/10/06)
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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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- Design and Synthesis of Alanine Triazole Ligands and Application in Promotion of Hydration, Allene Synthesis and Borrowing Hydrogen Reactions
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A new type of alanine triazole (ATA) ligand was found to be an efficient partner for the stabilization of gold(III), thus rendering improved stability and high catalytic activities in allene synthesis and hydration reactions through the 3,3′-arrangement of propargyl esters and propargyl alcohols. In addition to Au(I), ATA-gold(III) was also proven to be an effective catalyst in promoting the formation of allenes with high yields. Furthermore, alanine triazole ruthenium has exhibited excellent potential as a means to catalyze borrowing hydrogen of alcohols and amines, ketones and alcohols.
- Yang, Yongchun,Qin, Anni,Zhao, Keyan,Wang, Dawei,Shi, Xiaodong
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supporting information
p. 1433 - 1439
(2016/05/19)
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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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- 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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- 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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- Selective and recyclable rhodium nanocatalysts for the reductive N-alkylation of nitrobenzenes and amines with aldehydes
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Rhodium nanocatalysts were prepared and applied for the reductive N-alkylation of nitrobenzenes and amines to the corresponding secondary amines with aldehydes and ketones. Functional nitrobenzenes, such as nitrobenzenes with F, Cl, Br, CH3O and CH3 were transformed to the corresponding secondary amines in good to excellent yields. Moreover, the Rh@CN catalyzed N-alkylation of a series of primary amines with aldehydes and ketones also gave the corresponding secondary amines in high yields. The Rh@CN is heterogeneous, and can be reusable several times (at least 4 times) for the reductive N-alkylation of nitroarenes.
- Huang, Lei,Wang, Zhi,Geng, Longfei,Chen, Rizhi,Xing, Weihong,Wang, Yong,Huang, Jun
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p. 56936 - 56941
(2015/07/15)
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- A conjugated ketone as a catalyst in alcohol amination reactions under transition-metal and hetero-atom free conditions
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Here, we show the results of a molecular-defined conjugated ketone catalyzed alcohol amination reaction. Under the optimized reaction conditions, the yields to the desired products reached 98%. The reaction mechanism and kinetic study supposed that carbonyl-hydroxyl groups are the catalytically active sites, and the transfer-hydrogenation reactions progress via the recycling of carbonyl and hydroxyl groups. The catalytic process shows promise as an efficient and economic route for alcohol amination reactions.
- Dai, Xingchao,Cui, Xinjiang,Deng, Youquan,Shi, Feng
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p. 43589 - 43593
(2015/05/27)
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- Ruthenium(II) bis(hydrazone) complexes derived from 1,3,4-oxadiazoles: Synthesis, crystal structure and catalytic application in N-alkylation reactions
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1,3,4-Oxadiazoles (A-C) were derived via a series of reactions between isoniazid and salicylaldehydes. While reacting the oxadiazoles with [RuHCl(CO)(PPh3)3] in the presence of NaOH, mononuclear ruthenium(II) complexes bearing 'salen' type N,N′-bis(salicylidene)hydrazone ligands (1-3) were obtained. The oxadiazoles and ruthenium(II) complexes were characterized by analytical and spectral methods. The single crystal XRD analyses of complexes 1 and 2 suggested an octahedral geometry around ruthenium(II) ions in which the bis(hydrazone) act as mononegative bidentate ligands. It was also observed that the presence of an intramolecular hydrogen bonding between the hydroxyl proton and one of the azomethine nitrogens in all the complexes. Further, the complexes were proved as versatile catalysts for the N-alkylation of amines with alcohols under optimized reaction conditions.
- Prakash, Govindan,Ramachandran, Rangasamy,Nirmala, Muthukumaran,Viswanathamurthi, Periasamy,Sanmartin, Jesus
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supporting information
p. 203 - 210
(2015/01/30)
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- Insight into O2-promoted base-catalyzed N-alkylation of amines with alcohols
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A highly efficient and practical transition-metal-free CsOH/O2 catalyst system was developed for the N-alkylation of amines with alcohols under argon. This strategy was compatible with many alcohols and exhibits excellent functional group tolerance. More significantly, the selective formation of secondary amines was achieved in excellent yields. The detailed mechanistic study gave a clear understanding of the role of base and oxygen in the catalytic cycle.
- Wang, Chao,Chen, Changpeng,Han, Jian,Zhang, Jingyu,Yao, Yingming,Zhao, Yingsheng
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supporting information
p. 2972 - 2977
(2015/04/27)
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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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- 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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- Synthesis, structures of benzoxazolyl iridium(III) complexes, and applications on C-C and C-N bond formation reactions under solvent-free conditions: Catalytic activity enhanced by noncoordinating anion without silver effect
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Several new bisbenzoxazolyl iridium(III) complexes have been synthesized and characterized through X-ray crystallography. These complexes exhibit excellent catalytic activity in C-C and C-N bond formation reactions from the alkylation of amine with amine, amine with alcohol, ketone with alcohol, and alcohol with alcohol through a borrowing hydrogen reaction. Moreover, these iridium(III) complexes are effective catalysts for the alkylation of amine with alcohol and ketone with alcohol under solvent-free conditions. The catalytic activity of these complexes is greatly enhanced by noncoordinating, while the experiments have excluded the possibility of a "silver effect" (bimetallic catalysis or silver-assisted metal catalysis) from the experiments.
- Wang, Dawei,Zhao, Keyan,Xu, Chongying,Miao, Hongyan,Ding, Yuqiang
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p. 3910 - 3918
(2014/12/12)
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- Reinvestigating Raney nickel mediated selective alkylation of amines with alcohols via hydrogen autotransfer methodology
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An efficient, cost-effective use of Raney nickel (R-Ni) a widely used industrial catalyst for N-alkylation using alcohols is highlighted here. The work describes the scope and capability of R-Ni in hydrogen autotransfer reactions enabling its widespread use in the Chemical and Pharmaceutical industry. R-Ni of W4, T4, and W7 grades were prepared and evaluated for alkylation of amines. The best activity and selectivity for mono alkylation of amines were obtained using W4 R-Ni at 1:4 moles of amine to alcohol in xylene at reflux. T4 R-Ni also showed ability to form stable imines. The prepared R-Ni was also recycled and reused for N-alkylation reaction. The optimized methodology was applied for synthesis of Active Pharmaceutical ingredients Piribedil and Mepyramine. The simplicity and wide substrate scope makes this method a preferred Hydrogen Auto-transfer protocol for the alkylation of amines.
- Mehta, Astha,Thaker,Londhe,Nandan, Santosh R.
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p. 241 - 251
(2014/05/20)
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- Iron-catalyzed synthesis of secondary amines: On the way to green reductive aminations
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Amines represent important intermediates in chemical and biological processes. Herein, we describe the use of a nanostructured iron-based catalyst for the tandem reductive amination between nitroarenes and aldehydes using hydrogen as reductant. The nanostructured iron-catalyst is prepared by immobilization of an iron-phenanthroline complex onto a commercially available carbon support. In the reaction sequence a primary amine is formed in situ from the corresponding nitro compound. Reversible condensation with aldehydes forms the respective imines, which are finally reduced to the desired secondary amine. This synthesis of secondary amines is atom-economical and environmentally attractive using cheap and readily available organic compounds as starting materials.
- Stemmler, Tobias,Surkus, Annette-Enrika,Pohl, Marga-Martina,Junge, Kathrin,Beller, Matthias
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p. 3012 - 3016
(2015/09/28)
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- An efficient homogeneous gold(I) catalyst for N-alkylation of amines with alcohols by hydrogen autotransfer
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A new and highly efficient homogeneous [Ph3PAuCl]/AgOTf catalytic system was developed in N-alkylation reaction of primary amines with alcohols through a hydrogen autotransfer process. This Au(I) catalytic system shows excellent selectivity for mono-alkylation of primary amines with benzyl alcohol under moderate temperature of 100 °C (only secondary amines as product). The possible mechanism of this hydrogen autotransfer reaction with the catalytic system was proposed.
- Yang, Hongwei,Mao, Rongfang,Luo, Cuicui,Lu, Chunxu,Cheng, Guangbin
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p. 8829 - 8835
(2015/03/05)
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- Polymeric bimetallic catalyst-promoted in-water dehydrative alkylation of ammonia and amines with alcohols
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A dehydrative alkylation with three kinds of Ir/B heterobimetallic polymeric catalysts in water is reported. The polymeric heterobimetallic catalysts were readily prepared by ionic convolution of a poly(catechol borate) and iridium complexes. The N-alkylation of ammonia and amines with alcohols, as alkylating agents, was carried out with a heterogeneous catalyst (1 mol% Ir) at 100 °C without the use of organic solvents under aerobic and aqueous conditions to afford the corresponding alkylated amines in high yield. Georg Thieme Verlag Stuttgart New York.
- Yamada, Yoichim. A.,Ohta, Hidetoshi,Yuyama, Yoshinari,Uozumi, Yasuhiro
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p. 2093 - 2100
(2013/08/23)
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