- Reusable Co-nanoparticles for general and selectiveN-alkylation of amines and ammonia with alcohols
-
A general cobalt-catalyzedN-alkylation of amines with alcohols by borrowing hydrogen methodology to prepare different kinds of amines is reported. The optimal catalyst for this transformation is prepared by pyrolysis of a specific templated material, which is generatedin situby mixing cobalt salts, nitrogen ligands and colloidal silica, and subsequent removal of silica. Applying this novel Co-nanoparticle-based material, >100 primary, secondary, and tertiary amines includingN-methylamines and selected drug molecules were conveniently prepared starting from inexpensive and easily accessible alcohols and amines or ammonia.
- Beller, Matthias,Gawande, Manoj B.,Jagadeesh, Rajenahally V.,Kadam, Ravishankar G.,Li, Xinmin,Ma, Zhuang,Petr, Martin,Zbo?il, Radek,Zhou, Bei
-
p. 111 - 117
(2022/01/06)
-
- Cobalt encapsulated in N?doped graphene sheet for one-pot reductive amination to synthesize secondary amines
-
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
-
-
- Iron-catalyzed N-alkylation of aromatic amines via borrowing hydrogen strategy
-
Earth-abundant transition metals could be used as a noble metal replacement in catalysis not only for different catalytic reactivity but environmentally benign methodology. We report here on the iron-catalyzed synthesis of N-alkylated amines via borrowing hydrogen strategy and differently functionalized aniline derivatives are alkylated in good yields.
- Chen, Hui,Wang, Qingfu,Liu, Tingting,Chen, Haitao,Zhou, Duo,Qu, Fengbo
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p. 877 - 884
(2021/02/16)
-
- A base-free Chan–Lam reaction catalyzed by an easily assembled Cu(II)-carboxylate metal-organic framework
-
A new copper(II) metal-organic framework is constructed as a sustainable copper heterogeneous catalyst. Cu-DPTCA, with high catalytic activity, can effectively promote the Chan–Lam coupling reaction of arylboronic acids and amines without adding any base or additive.
- Ma, Ruixuan,Qin, Jianhua,Shi, Lei,Zhang, Xinhai
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p. 795 - 799
(2021/07/06)
-
- Atomically dispersed Rh on hydroxyapatite as an effective catalyst for tandem hydroaminomethylation of olefins
-
Tandem hydroaminomethylation is an efficient and green route for one-pot synthesis of amines directly from olefins. Herein, heterogeneous hydroxyapatite (HAP) supported single-atom Rh catalyst was prepared and used for tandem hydroaminomethylation of olefins. Characterization techniques confirmed the atomic dispersion of Rh species on HAP. Up to 99% conversion of 1-hexene with high selectivity to the desired amines (93.2%) was obtained over 0.5Rh1/HAP catalyst. Mechanism study demonstrated that the first hydroformylation step during the tandem catalytic process was rate-determining. Compared with the Rh nanoparticles on other oxide supports (Mg3Al, MgO and Al2O3), the atomically dispersed Rh sites on HAP ensured the high hydroformylation activity, thereby guaranteed the outstanding catalytic performance for the total tandem process. Furthermore, various corresponding amines can be obtained with satisfactory yields over 0.5Rh1/HAP catalyst from a wide scope of olefins or amines substrates.
- Gun, Gong,Li, Liusha,Li, Xiao,Lin, Tiejun,Qin, Tingting,Zhong, Liangshu
-
-
- A highly efficient Co-based catalyst fabricated by coordination-assisted impregnation strategy towards tandem catalytic functionalization of nitroarenes with various alcohols
-
A well-defined hexamethylenetetramine (abbreviated as HMTA) based two-dimensional (2D) MOFs metalloligand (termed Zn-HMTA), with free uncoordinated tertiary amine groups, has been synthesized via solution diffusion method for the first time. The crystal structure of 2D Zn-HMTA metalloligand was determined by the single crystal X-ray diffraction (SCXRD). The SCXRD and X-ray photoelectron spectroscopy (XPS) analyses have revealed that the 2D Zn-HMTA metalloligand is rich in- free tertiary amine groups, which are of strong coordination ability to transition metal ions (e.g. Ni2+, Co2+, Zn2+, Cu2+). As a result, a 2D bimetallic Co@Zn-HMTA MOFs was synthesized via coordination-assisted impregnation (CAI) strategy attributed to the unique feature of strong coordinated ability of free tertiary amine groups. Furthermore, a series of self-supported Co-ZnO-CN nanocatalysts were afforded upon the as-synthesized Co@Zn-HMTA MOFs served as a self-sacrificial template for pyrolysis at different temperatures. The optimized catalyst (termed as Co-ZnO@CN-CAI) demonstrated the excellent catalytic performance for hydrogenation-alkylation tandem reaction in comparison with the classic ZnO@CN composite (derived from Zn-HMTA MOFs) supported metallic Co catalyst (Co-ZnO@CN-IWI) prepared by incipient wetness impregnation method. Moreover, the kinetic study was also performed to confirm that the alkylation is the rate-determining step in the hydrogenation-alkylation tandem reaction. The origin of enhanced catalytic performance of Co-ZnO@CN-CAI and the role of Co@Zn-HMTA MOFs precursor have been explored by way of various characterizations, e.g. HADDF-STEM-EDS, SEM-EDS, 13C MAS NMR, XRD, Raman and XPS, etc. It is anticipated that the prepared low-cost and easily prepared 2D Zn-HMTA metalloligand will become a general template for synthesis of highly self-supported catalysts with coordination-assisted impregnation strategy (CAI) for various catalytic reactions.
- Li, Guangming,Li, Jingfang,Li, Weizuo,Li, Xuewei,Li, Zhibin,Mao, Guijie,She, Wei,Wang, Jing
-
p. 462 - 474
(2021/11/11)
-
- Base-mediated cascade amidination/: N -alkylation of amines by alcohols
-
A base-mediated cascade amidination/N-alkylation reaction of amines by alcohols has been developed. For the first time, nitriles have been identified as an efficient and benign water acceptor reagent in N-alkylation. Notably, the procedure tolerates a series of functional groups, such as methoxyl, halo, vinyl and hetero groups, providing a convenient method to construct different substituted diamino compounds, 15N labeled amine and could be scaled up to 1 mol scale offering 138.7 g of the desired product in good yield in one-pot. Mechanistic studies provided strong evidence for the amidination of amines with nitriles facilitated by t-BuOK.
- Hu, Mao-Lin,Jia, Xiaofei,Liang, Zuyu,Lu, Fenghong,Zhang, Chunyan,Zhang, Guoying
-
supporting information
p. 10489 - 10492
(2020/10/02)
-
- C–N Cross-coupling Reactions of Amines with Aryl Halides Using Amide-Based Pincer Nickel(II) Catalyst
-
Abstract: An approach to C–N cross-coupling reactions of aryl halides with amines in the presence of an amide-based pincer nickel(II) catalyst (2) is described. For 3?h reactions at 110?°C with 0.2?mol% catalyst, aryl bromides gave higher turnover numbers (TON) than the corresponding chlorides or iodides. Both primary and secondary amines could be used with the former giving higher TON. However, sterically hindered amines showed lower TON. In elucidating the mechanism of this nickel complex-catalyzed C–N cross coupling reaction it was found that the rate of reaction was unchanged in the presence of radical quenchers and a plausible Ni(I)–Ni(III) pathway is proposed. Graphic Abstract: [Figure not available: see fulltext.]Nickel pincer catalyst proved to be excellent catalyst for the C-N cross-coupling reaction with the high turnover number (TON) for 1° and 2° amines and different nonactivated aryl halides under optimum conditions.
- Albkuri, Yahya M.,RanguMagar, Ambar B.,Brandt, Andrew,Wayland, Hunter A.,Chhetri, Bijay P.,Parnell, Charlette M.,Szwedo, Peter,Parameswaran-Thankam, Anil,Ghosh, Anindya
-
p. 1669 - 1678
(2019/12/27)
-
- Borrowing Hydrogen-Mediated N-Alkylation Reactions by a Well-Defined Homogeneous Nickel Catalyst
-
We report herein a well-defined and bench-stable azo-phenolate ligand-coordinated nickel catalyst which can efficiently execute N-alkylation of a variety of anilines by alcohol. We demonstrate that the redox-active azo ligand can store hydrogen generated during alcohol oxidation and redelivers the same to an in-situ-generated imine bond to result in N-alkylation of amines. The reaction has wide scope, and a large array of alcohols can directly couple to a variety of anilines. Mechanistic studies including deuterium labeling to the substrate establishes the borrowing hydrogen method from alcohols and pinpoints the crucial role of the redox-active azo moiety present on the ligand backbone. Isolation of the ketyl intermediate in its trapped form with a radical quencher and higher kH/kD for the alcohol oxidation step suggest altogether a hydrogen-atom transfer (HAT) to the reduced azo backbone to pave alcohol oxidation as opposed to the conventional metal-ligand bifunctional mechanism. This example clearly demonstrates that an inexpensive base metal catalyst can accomplish an important coupling reaction with the help of a redox-active ligand backbone.
- Bains, Amreen K.,Kundu, Abhishek,Yadav, Sudha,Adhikari, Debashis
-
p. 9051 - 9059
(2019/10/02)
-
- Ru-Catalyzed Deoxygenative Transfer Hydrogenation of Amides to Amines with Formic Acid/Triethylamine
-
A ruthenium(II)-catalyzed deoxygenative transfer hydrogenation of amides to amines using HCO2H/NEt3 as the reducing agent is reported for the first time. The catalyst system consisting of [Ru(2-methylallyl)2(COD)], 1,1,1-tris(diphenylphosphinomethyl) ethane (triphos) and Bis(trifluoromethane sulfonimide) (HNTf2) performed well for deoxygenative reduction of various secondary and tertiary amides into the corresponding amines in high yields with excellent selectivities, and exhibits high tolerance toward functional groups including those that are reduction-sensitive. The choice of hydrogen source and acid co-catalyst is critical for catalysis. Mechanistic studies suggest that the reductive amination of the in situ generated alcohol and amine via borrowing hydrogen is the dominant pathway. (Figure presented.).
- Pan, Yixiao,Luo, Zhenli,Xu, Xin,Zhao, Haoqiang,Han, Jiahong,Xu, Lijin,Fan, Qinghua,Xiao, Jianliang
-
supporting information
p. 3800 - 3806
(2019/07/12)
-
- Manganese-Catalyzed and Base-Switchable Synthesis of Amines or Imines via Borrowing Hydrogen or Dehydrogenative Condensation
-
The use of earth-abundant transition metals as a noble metal replacement in catalysis is especially interesting if different catalytic reactivity is observed. We report, here, on the selective manganese-catalyzed base-switchable synthesis of N-alkylated amines or imines. In both reactions, borrowing hydrogen/hydrogen autotransfer (N-alkyl amine formation) or dehydrogenative condensation (imine formation), we start from the same amines and alcohols and use the same Mn precatalyst. The key is the presence of a potassium base to prefer N-alkylation and a sodium base to permit imine formation. Both bases react with the manganese hydride via deprotonation. The potassium manganate hydride reacts about 40 times faster with an imine to give the corresponding amine than the sodium manganate hydride. The selectivity seems unique for manganese complexes. We observe a broad scope with a complete product overlap, all amine alcohol combinations can be converted into an N-alkyl amine or an imine, and a good functional group tolerance.
- Fertig, Robin,Irrgang, Torsten,Freitag, Frederik,Zander, Judith,Kempe, Rhett
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p. 8525 - 8530
(2018/09/06)
-
- Cobalt-Rhodium Heterobimetallic Nanoparticle-Catalyzed N-Alkylation of Amines with Alcohols to Secondary and Tertiary Amines
-
Without the requirement for base or other additives, Co2Rh2/C can selectively catalyze both mono- and bis-N-alkylation through the coupling of simple alcohols with amines, yielding a range of secondary and tertiary amines in good to excellent isolated yields. The reaction can be applied to benzyl alcohol with optically active 1-phenylethan-1-amines, and secondary amines were isolated in quantitative yields with an excellent enantiomeric excess (ee > 94%). Selectivity is achieved by varying the reaction temperature and amount of catalyst used. This catalytic system has several advantages including eco-friendliness and a simple workup procedure. The catalyst can be successfully recovered and reused ten times without any significant loss of activity.
- Chung, Hyunho,Chung, Young Keun
-
p. 8533 - 8542
(2018/07/30)
-
- Method for preparing secondary aromatic amine or tertiary aromatic amine by conducting amination on aryl halide or alkyl halide
-
The invention discloses a method for preparing secondary aromatic amine or tertiary aromatic amine by conducting amination on aryl halide or alkyl halide. That is to say, the alkyl halide or the arylhalide and organic amine are mixed according to a certain ratio, and under light irradiation, C-N coupling reaction is carried out, so that a corresponding target product is generated for preparing the secondary amine or the tertiary amine. Compared with existing synthesis technologies, the method has the advantages that the aryl halide or the alkyl halide which is cheap and easy to get is selected as a reaction substrate, the method has good universality for different organic amine separately, moreover, the product selectivity is high, and separation and purification are easy; moreover, the synthesis method does not need to be conducted under severe conditions of high temperature and the like, a green and sustainable light source is adopted as driving force, the atom economy is high, andthe method has wide application prospects.
- -
-
Paragraph 0029-0035; 0160; 0124; 0125; 0162
(2019/01/14)
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- An efficient and recyclable ionic diphosphine-based Ir-catalyst for hydroaminomethylation of olefins with H2O as the hydrogen source
-
Hydroaminomethylation of olefins with H2O as the hydrogen source was accomplished over an Ir-catalyst with the involvement of an ionic diphosphine (L6). The use of H2O as the hydrogen source could completely inhibit the hydrogenation
- Liu, Huan,Yang, Da,Wang, Dong-Liang,Wang, Peng,Lu, Yong,Giang, Vo-Thanh,Liu, Ye
-
supporting information
p. 7979 - 7982
(2018/07/25)
-
- One-pot Reductive Amination of carbonyl Compounds with Nitro Compounds by Transfer Hydrogenation over Co–Nx as catalyst
-
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
-
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
-
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)
-
- Flow synthesis of secondary amines over Ag/Al2O3 catalyst by one-pot reductive amination of aldehydes with nitroarenes
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An alumina-supported silver catalyst was investigated in the one-pot reductive amination of aldehydes with nitroarenes in a continuous flow reactor using molecular hydrogen as a reducing agent. A series of secondary amines containing alkyl, OH, OCH3, Cl, Br and CC groups was synthesized in good to excellent yields. The yield of the secondary amine depends on the rate of formation of an intermediate imine. It was shown that the accumulation of carbonaceous deposits on the catalyst is the main reason of catalyst deactivation. The spent catalyst can be easily regenerated and reused without losing catalytic activity.
- Artiukha, Ekaterina A.,Nuzhdin, Alexey L.,Bukhtiyarova, Galina A.,Bukhtiyarov, Valerii I.
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p. 45856 - 45861
(2017/10/06)
-
- Synthesis of secondary amines by reductive amination of aldehydes with nitroarenes over supported copper catalysts in a flow reactor
-
Supported copper catalysts were investigated for the one-pot reductive amination of aldehydes with nitroarenes in a continuous flow reactor. This process is considered advantageous compared to current traditional methods, which present several drawbacks, such as toxicity of reducing or alkylation agent, lack of monoalkylation selectivity and large amounts of waste produced. Various secondary amines were synthesized in good to excellent yields in the reactions of aliphatic aldehydes with nitroarenes using molecular hydrogen as a reducing agent. It was found that the yield of secondary amine depends on the rate of formation of intermediate imine.
- Nuzhdin, Alexey L.,Artiukha, Ekaterina A.,Bukhtiyarova, Galina A.,Derevyannikova, Elizaveta A.,Bukhtiyarov, Valerii I.
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p. 108 - 113
(2017/09/15)
-
- An Efficient and Selective Nickel-Catalyzed Direct N-Alkylation of Anilines with Alcohols
-
Herein, we developed an efficient and selective nickel-catalyzed monoalkylation of various primary alcohols with aryl and heteroaryl amines together with diols and amino alcohol derivatives. Notably, the catalytic protocol consisting of an earth-abundant and non-precious NiBr2/L1 system enables the transformations in the presence of hydroxyl, alkene, nitrile, and nitro functionalities. As a highlight, we have demonstrated the alkylation of diamine, intramolecular cyclization to N-heterocycles, and functionalization of complex vitamin E, an (±)-α-tocopherol derivative. Preliminary mechanistic studies revealed the participation of a benzylic C-H bond in the rate-determining step.
- Vellakkaran, Mari,Singh, Khushboo,Banerjee, Debasis
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p. 8152 - 8158
(2017/12/08)
-
- Photometric Characterization of the Reductive Amination Scope of the Imine Reductases from Streptomyces tsukubaensis and Streptomyces ipomoeae
-
Imine reductases (IREDs) have emerged as promising enzymes for the asymmetric synthesis of secondary and tertiary amines starting from carbonyl substrates. Screening the substrate specificity of the reductive amination reaction is usually performed by time-consuming GC analytics. We found two highly active IREDs in our enzyme collection, IR-20 from Streptomyces tsukubaensis and IR-Sip from Streptomyces ipomoeae, that allowed a comprehensive substrate screening with a photometric NADPH assay. We screened 39 carbonyl substrates combined with 17 amines as nucleophiles. Activity data from 663 combinations provided a clear picture about substrate specificity and capabilities in the reductive amination of these enzymes. Besides aliphatic aldehydes, the IREDs accepted various cyclic (C4–C8) and acyclic ketones, preferentially with methylamine. IR-Sip also accepted a range of primary and secondary amines as nucleophiles. In biocatalytic reactions, IR-Sip converted (R)-3-methylcyclohexanone with dimethylamine or pyrrolidine with high diastereoselectivity (>94–96 % de). The nucleophile acceptor spectrum depended on the carbonyl substrate employed. The conversion of well-accepted substrates could also be detected if crude lysates were employed as the enzyme source.
- Matzel, Philipp,Krautschick, Lukas,H?hne, Matthias
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p. 2022 - 2027
(2017/10/07)
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- Carbon dioxide transformation in imidazolium salts: Hydroaminomethylation catalyzed by Ru-complexes
-
The catalytic species generated by dissolving Ru3(CO)12 in the ionic liquids 1-n-butyl-3-methyl-imidazolium chloride or 1-n-butyl-2,3-dimethyl-imidazolium chloride are efficient multifunctional catalysts for: (a) reverse water-gas shift, (b) hydroformylation of alkenes, and (c) reductive amination of aldehydes. Thus the reaction of alkenes with primary or secondary amines (alkene/amine, 1:1) under CO2/H2 (1:1) affords the hydroamino-methylations products in high alkene conversions (up to 99%) and selectivities (up to 96%). The reaction proceeds under relatively mild reaction conditions (120 °C, 60 bar = 6 MPa) and affords selectively secondary and tertiary amines. The presence of amine strongly reduces the alkene hydrogenation competitive pathway usually observed in the hydroformylation of terminal alkenes by Ru complexes. The catalytic system is also highly active for the reductive amination of aldehydes and ketones yielding amines in high yields (> 90%).
- Ali, Meher,Gual, Aitor,Ebeling, Gunter,Dupont, Jairton
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p. 2129 - 2134
(2017/07/25)
-
- Scalable synthesis of secondary and tertiary amines by heterogeneous Pt-Sn/γ-Al2O3catalyzed N-alkylation of amines with alcohols
-
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
-
supporting information
p. 8516 - 8521
(2016/11/28)
-
- Iron-catalysed sequential reaction towards α-aminonitriles from secondary amines, primary alcohols and trimethylsilyl cyanide
-
We have developed a one-pot iron-catalysed sequential reaction of secondary amines with primary alcohols, trimethylsilyl cyanide and TBHP under mild reaction conditions to give the corresponding α-aminonitriles.
- Shen, Hang,Hu, Liangzhen,Liu, Qing,Hussain, Muhammad Ijaz,Pan, Jing,Huang, Mingming,Xiong, Yan
-
supporting information
p. 2776 - 2779
(2016/02/19)
-
- One-pot reductive amination of aldehydes with nitroarenes over an Au/Al2O3 catalyst in a continuous flow reactor
-
One-pot reductive amination of aromatic and aliphatic aldehydes with nitroarenes over an Au/Al2O3 catalyst in a continuous flow reactor using molecular hydrogen as a reducing agent was performed. Various secondary aromatic amines were obtained in good to excellent yields.
- Artiukha,Nuzhdin,Bukhtiyarova,Zaytsev, S. Yu.,Plyusnin,Shubin, Yu. V.,Bukhtiyarov
-
p. 4741 - 4745
(2015/10/05)
-
- USE OF COMPOSITIONS OBTAINED BY CALCINING PARTICULAR METAL-ACCUMULATING PLANTS FOR IMPLEMENTING CATALYTICAL REACTIONS
-
The use of metal-accumulating plants for implementing chemical reactions especially catalytical reactions.
- -
-
Paragraph 0855
(2016/01/25)
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- Solvent free acid catalysed direct N-alkylation of amines with alcohols using Al grafted MCM-41
-
The catalytic activity of Al grafted MCM-41 (Al-MS) was explored for solvent free acid catalysed direct N-alkylation of amines using alcohols as green alkylating agent to establish a clean method for synthesis of N-alkylated amines. The study revealed that acidity of Al-MS catalyst, reaction conditions and substrate's (amines and alcohols) nature are important factors influencing the N-alkylation reaction. The Al grafted MCM-41 with Si/Al molar ratio of 5 showed excellent activity for N-alkylation of amines with alcohols. The reusability of spent catalyst regenerated by simple washing with acetone was demonstrated for subsequent four reaction cycles.
- Tayade, Kamlesh N.,Mishra, Manish,Munusamy,Somani, Rajesh S.
-
-
- Bifunctional iridium-(2-aminoterephthalate)-Zr-MOF chemoselective catalyst for the synthesis of secondary amines by one-pot three-step cascade reaction
-
A simple and efficient method for the synthesis of N-alkyl amines via a cascade reaction (hydrogenation + reductive amination) using a new recyclable hybrid catalyst that combines the catalytic power of transition metal complexes with the architecture of metal organic frameworks (MOFs).
- Pintado-Sierra, Mercedes,Rasero-Almansa, Antonia M.,Corma, Avelino,Iglesias, Marta,Sanchez, Felix
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p. 137 - 145
(2013/03/28)
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- Reduction of hydrazines to amines with low-valent titanium reagent
-
The N,N bond cleavage in hydrazines to amines via low-valent titanium reagent prepared in situ by treatment of TiCl4 with Mg powder in THF or CH2Cl2-Et2O is described. The reaction proceeds smoothly under mild conditions to afford amines in good to excellent yields with diverse functional group tolerance such as chloride, methoxyl, benzyloxyl, ester, acyl, as well as C,C double bonds and benzyl-nitrogen bonds. ARKAT-USA, Inc.
- Ren, Fang,Zhang, Yan,Hu, Lan,Luo, Meiming
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p. 165 - 173
(2013/06/27)
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- Ligand-free C-N bond formation in aqueous medium using a reusable Cu-Mn bimetallic catalyst
-
A general ligand-free protocol has been described for the recyclable and reusable Cu-Mn catalyzed C-N bond forming cross coupling reaction of arylboronic acids with various amines to form N-arylated amine products in aqueous medium affording excellent yields under ambient conditions, in 3-4 h.
- Sawant, Sanghapal D.,Srinivas, Mahesuni,Aravinda Kumar,Lakshma Reddy,Singh, Parvinder Pal,Singh, Baldev,Sharma, Amit Kumar,Sharma,Vishwakarma, Ram A.
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p. 5351 - 5354
(2013/09/12)
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- Selective hydroaminomethylation of olefins using simple and efficient Rh-phosphinite complex catalyst
-
Hydroaminomethylation of various olefins with primary and secondary amines was carried out using a simple and efficient rhodium-phosphinite complex catalyst. The influence of various reaction parameters including the effects of temperature, pressure, catalyst loading, time and solvents has been investigated. The present protocol is general with wider substrate applicability for the synthesis of an important class of aliphatic amines and arylethylamines. High activity and selectivity for amines was achieved with a very good substrate/catalyst molar ratio (turnover number 2500) under mild reaction conditions. Copyright
- Khan, Shoeb R.,Bhanage, Bhalchandra M.
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p. 711 - 715
(2013/12/04)
-
- Multisite solid (NHC)NN-Ru-catalysts for cascade reactions: Synthesis of secondary amines from nitro compounds
-
Supported ruthenium complexes based on electron-rich (NHC)NN-pincer-type ligands selectively catalyze the formation of substituted amines from nitroaromatics and carbonyl compounds through a series of consecutive steps which involves the reduction of nitro group to amine, the formation of an imine or iminium ion intermediate, followed by in situ reduction to an alkylated amine of higher order in a single operation. Solid complexes result active and recyclable catalysts and no deactivation was observed after repeated recycling.
- Del Pozo, Carolina,Corma, Avelino,Iglesias, Marta,Sanchez, Felix
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experimental part
p. 110 - 116
(2012/08/08)
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- One-pot synthesis of aniline derivatives from nitroarenes under mild conditions promoted by a recyclable polymer-supported palladium catalyst
-
This work describes the one-pot direct reductive amination of carbonyl compounds with nitroarenes promoted by a polymer supported palladium catalyst, in the presence of molecular hydrogen as the reductant. This methodology is applicable, with slight differences, to both aliphatic and aromatic aldehydes. The operational simplicity, the mild reaction conditions, the high yields and the good recyclability of the supported catalyst are major advantages of this method. TEM observations of the catalyst showed that the active species are palladium nanoparticles having a size distribution centered at 5 nm within the polymeric support.
- Dell'Anna, Maria Michela,Mastrorilli, Piero,Rizzuti, Antonino,Leonelli, Cristina
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scheme or table
p. 134 - 140
(2012/03/27)
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- Palladium(II) acetate as catalyst for the N-alkylation of aromatic amines, sulfonamides, and related nitrogenated compounds with alcohols by a hydrogen autotransfer process
-
Palladium(II) acetate is a versatile, inexpensive, and simple catalyst for the selective N-monoalkylation of amino derivatives with poor nucleophilic character, such as aromatic and heteroaromatic amines as well as carboxamides, sulfonamides, and phosphazenes, using, in all cases, primary alcohols as the initial source of the electrophile, through a hydrogen autotransfer process. The regioselectivity of the benzothiazol-2-amine alkylation is contrary to that found using halogenated electrophiles.
- Martinez-Asencio, Ana,Yus, Miguel,Ramon, Diego J.
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experimental part
p. 3730 - 3740
(2011/12/21)
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- Reduction of hydrazines to amines with aqueous solution of titanium(iii) trichloride
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N-N bond cleavage in hydrazines is widely used in the preparation of amines and thus occupies a significant place in organic synthesis. In this paper, we report a new method for the reductive cleavage of N-N bonds in hydrazines by commercially available and cheap aqueous titanium(iii) trichloride. The reaction proceeds smoothly under a broad pH range from acidic to neutral and basic conditions to afford amines in good yields. This method is compatible with substrates containing functionalities such as C-C double bonds, benzyl-nitrogen bonds, benzyloxy and acyl groups. The Royal Society of Chemistry 2011.
- Zhang, Yan,Tang, Qiang,Luo, Meiming
-
supporting information; experimental part
p. 4977 - 4982
(2011/08/05)
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- N-Alkylation of poor nucleophilic amines and derivatives with alcohols by a hydrogen autotransfer process catalyzed by copper(II) acetate: Scope and mechanistic considerations
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Copper(II) acetate is a versatile, cheap and simple catalyst for the selective N-monoalkylation of amino derivatives with poor nucleophilic character, such as aromatic and heteroaromatic amines as well as carboxamides, phosphinamides, sulfonamides, and phosphazenes, using in all cases primary alcohols as initial source of the electrophiles, through a hydrogen autotransfer process. In the case of sulfonamides, the monoalkylation process followed by a naphthalene-catalyzed reductive deprotection gives primary amines, which is an indirect alternative to the direct monoalkylation of ammonia. A study of the reaction using deuterium labelled reagents was performed, indicating that the dehydrogenation and hydrogenation steps do not take placed on the same copper-atom coordination sphere, with the condensation step occurring out of the dehydrogenating catalytic species.
- Martínez-Asencio, Ana,Ramón, Diego J.,Yus, Miguel
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experimental part
p. 3140 - 3149
(2011/05/06)
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- Copper iodide as a recyclable catalyst for Buchwald N-arylation
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An experimentally simple, efficient, and inexpensive catalyst system was developed for the N-arylation of indole, substituted indoles, pyrazole, imidazole, benzamide, morpholine, benzimidazole, thiobenzamide, aniline, benzylaniline, octylaniline, heptylaniline, and cyclohexylaniline with aryl iodides and bromides by using CuI as catalyst, trans-1,2-diaminocyclohexane (L1) as ligand, K2CO3 as base, and water as solvent at 80 °C. The yields were excellent, and the catalytic system was recyclable up to four times without loss of catalytic activity. Arylated amines are green protocol that avoids hazardous and moisture-sensitive catalysts. The catalytic system can be recycled up to four times without loss of catalytic activity. Copyright
- Swapna, Kokkirala,Murthy, Sabbavarapu Narayana,Nageswar, Yadavalli Venkata Durga
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experimental part
p. 6678 - 6684
(2011/02/25)
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- Recyclable heterogeneous iron catalyst for C-N cross-coupling under ligand-free conditions
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(Chemical Equation Presented) An efficient and ligand-free C-N cross-coupling of aryl halides with various heterocycles using Fe/Cg as a recyclable catalyst is reported. The yields are excellent to moderate. 2009 American Chemical Society.
- Swapna,Vijay Kumar,Prakash Reddy,Rama Rao
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supporting information; experimental part
p. 7514 - 7517
(2009/12/28)
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- An unusual peroxide-mediated amination of cycloalkanes with nitroarenes
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A direct amination of simple cycloalkanes with nitroarenes mediated by peroxides has been discovered. Various secondary arylamines were obtained efficiently from cycloalkanes. The reaction tolerates a wide range of functionalities as well as aqueous condi
- Deng, Guojun,Chen, Wenwen,Li, Chao-Jun
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supporting information; experimental part
p. 353 - 356
(2009/10/25)
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- A new method for N-N bond cleavage of N,N-disubstituted hydrazines to secondary amines and direct ortho amination of naphthol and its analogues
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An unexpected reaction of N,N-disubstituted hydrazine with naphthol and its analogues under simply thermal conditions has been disclosed. 2-Naphthol reacted with various N,N-disubstituted hydrazines under argon to afford 1-amino-2-naphthol and the corresponding secondary amines in excellent yields. Ortho amination of 2-naphthols, hydroxyquinoline, and naphthalenamine occurred when they reacted with N-methyl-N-phenylhydrazine. Copyright
- Tang, Qiang,Zhang, Chao,Luo, Meiming
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p. 5840 - 5841
(2008/09/19)
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- Direct reductive amination of carbonyl compounds with primary/secondary amines using recyclable water-soluble FeII/EDTA complex as catalyst
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Direct reductive amination of aliphatic, aromatic and heterocyclic carbonyl compounds with primary/secondary amines is reported with water-soluble FeII/EDTA complex as a catalyst using low-pressure molecular hydrogen in a biphasic media. The catalyst is highly selective, recyclable and is an excellent replacement for expensive noble metal catalysts or stoichiometric reducing agents.
- Bhor, Malhari D.,Bhanushali, Mayur J.,Nandurkar, Nitin S.,Bhanage, Bhalchandra M.
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p. 965 - 969
(2008/09/17)
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- An efficient base-free N-arylation of imidazoles and amines with arylboronic acids using copper-exchanged fluorapatite
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(Chemical Equation Presented) N-Arylation of imidazoles and amines with arylboronic acids was accomplished with copper-exchanged fluorapatite (Cu-FAP) in methanol at room temperature. The products N-arylimidazoles and N-arylamines were isolated in good to excellent yields. A variety of arylboronic acids were converted to the corresponding N-arylimidazoles and N-arylamines, demonstrating the versatility of the reaction.
- Kantam, M. Lakshmi,Venkanna, Gopaldasu T.,Sridhar, Chidara,Sreedhar, Bojja,Choudary, Boyapati M.
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p. 9522 - 9524
(2007/10/03)
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- A novel strategy for N-alkylation of primary amines+
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N-alkylation of primary amines has been carried out with alkylbromide using commercial Me2SO and K2CO3 as a base. This process offers a method of selection for obtaining either mono or dialkyl amines.
- Srivastava, Sanjay K.,Chauhan, Prem Man Singh,Bhaduri, Amiya P.
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p. 2085 - 2091
(2007/10/03)
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