- 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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- Catalyst-free photoinduced selective oxidative C(sp3)-C(sp3) bond cleavage in arylamines
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Due to the directional nature of sp3-hybridized orbitals and the absence of π-orbitals, the oxidative cleavage of the kinetically and thermodynamically stable C(sp3)-C(sp3) bond is extremely difficult and remains scarcely explored. In this work, under the double argument of quantum mechanics (QM) computations and meticulous experiments on our well-designed C-C single bond cleavage mechanism, we discovered a means of photoinduced selective oxidative C(sp3)-C(sp3) bond cleavage in arylamines, easily achieved by simple visible light irradiation using O2as a benign oxidant under very mild conditions. The utility of our methodology was demonstrated by the C(sp3)-C(sp3) bond cleavage in morpholine/piperazine arylamines with excellent functional group tolerance. Importantly, our methodology is noteworthy, not only in that it does not require any catalysts, but also in that it provides valuable possibilities for the scalable functionalization of clinical drugs and natural products.
- Duan, Wentao,Lian, Qi,Wang, Songping,Wei, Wentao,Zhou, Jingwei
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supporting information
p. 3261 - 3267
(2021/05/21)
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- Cooperative catalysis of molybdenum with organocatalysts for distribution of products between amines and imines
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Multi-amino groups and nitrogen donors compound was discovered as an organocatalyst for N-alkylation of alcohols with amines in the presence of Mo(CO)6. The Mo(CO)6/organocatalyst binary system has shown to be a highly active catalyst for the N-alkylation reaction between alcohols and amines with excellent tolerance of variable starting materials bearing different functional groups. Of particular note, this method possessing a superiority selectivity in the synthesis of N-alkylated amines or imines, which can be controlled by the reaction temperature. The cooperative catalysis mechanism in combination of Mo(CO)6 with organocatalyst was elucidated by control experiments.
- Wu, Di,Bu, Qingqing,Guo, Cheng,Dai, Bin,Liu, Ning
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- Pd catalysts supported on dual-pore monolithic silica beads for chemoselective hydrogenation under batch and flow reaction conditions
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Two different types of palladium catalysts supported on dual-pore monolithic silica beads [5% Pd/SM and 0.25% Pd/SM(sc)] for chemoselective hydrogenation were developed. Alkyne, alkene, azide, and nitro functionalities and the aromatic N-Cbz protecting group were chemoselectively hydrogenated using 5% Pd/SM. On the other hand, 0.25% Pd/SM(sc) showed unique and higher hydrogenation catalyst activity toward a wide variety of reducible functionalities. Furthermore, the catalyst activities of both 5% Pd/SM and 0.25% Pd/SM(sc) under flow hydrogenation conditions were also evaluated. A pre-packed 5% Pd/SM cartridge could be used continuously for at least 72 h without any loss of catalyst activity. The 0.2% Pd/SM(sc) catalyst prepacked in a cartridge showed high catalyst activity for the flow hydrogenation of trisubstituted alkenes under mild reaction conditions. This journal is
- Yamada, Tsuyoshi,Ogawa, Aya,Masuda, Hayato,Teranishi, Wataru,Fujii, Akiko,Park, Kwihwan,Ashikari, Yosuke,Tomiyasu, Noriyuki,Ichikawa, Tomohiro,Miyamoto, Riichi,Bai, Hongzhi,Matsuyama, Kiyoshi,Nagaki, Aiichiro,Sajiki, Hironao
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p. 6359 - 6367
(2020/11/03)
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- Development of Carbon-Neutral Cellulose-Supported Heterogeneous Palladium Catalysts for Chemoselective Hydrogenation
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Palladium catalysts immobilized on cellulose particles (Pd/CLP) and on a cellulose-monolith (Pd/CLM) were developed. These composites were applied as hydrogenation catalysts and their catalyst activities were evaluated. Although both catalysts catalyzed the deprotection of benzyloxycarbonyl-protected aromatic amines (Ar-N-Cbz) and aromatic benzyl esters (Ar-CO2Bn), only Pd/CLM could accomplish the hydrogenolysis of aliphatic-N-Cbz and aliphatic-CO2Bn protective groups. The difference in the physical structure of the cellulose supports induced unique chemoselectivity. Aliphatic-N-Cbz and aliphatic-CO2Bn groups were tolerated under the Pd/CLP-catalyzed hydrogenation conditions, while Ar-N-Cbz, Ar-CO2Bn, alkene, alkyne, azido and nitro groups could be smoothly reduced.
- Yamada, Tsuyoshi,Teranishi, Wataru,Park, Kwihwan,Jiang, Jing,Tachikawa, Takumu,Furusato, Shinichi,Sajiki, Hironao
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p. 4052 - 4058
(2020/07/13)
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- Reductive Alkylation of Amines with Carboxylic Ortho Esters
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We have demonstrated for the first time that carboxylic ortho esters could be used as an alkylating agent in the reductive alkylation of amines. A variety of amines, including amino acid esters, were alkylated affording mono-alkylated products with high selectivity in practical to high yields using standard heterogeneous catalysts. By applying acyclic ortho esters alkylation was completed at room temperature. (Figure presented.).
- Kadyrov, Renat,Moebus, Konrad
-
supporting information
p. 3352 - 3357
(2020/07/04)
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- C–N Cross-coupling Reactions of Amines with Aryl Halides Using Amide-Based Pincer Nickel(II) Catalyst
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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
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p. 1669 - 1678
(2019/12/27)
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- Simple reversible fixation of a magnetic catalyst in a continuous flow system: Ultrafast reduction of nitroarenes and subsequent reductive amination using ammonia borane
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Continuous reductive amination of aldehydes with nitroarenes over a Pd-Pt-Fe3O4 catalyst was performed. We used NH3BH3 as not only a hydrogen source for nitro reduction, but also a reductant for imine reduction. Secondary aromatic amines were obtained in the continuous flow reaction in good to excellent yields.
- Byun, Sangmoon,Cho, Ahra,Kang, Dong Yun,Kim, B. Moon,Kim, Ha Joon,Kim, Hong Won,Kim, Seong Min,Lei, Cao,Park, Jin Kyoon
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p. 944 - 949
(2020/03/11)
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- Catalyst-Free Electrosynthesis of Benzimidazolones through Intramolecular Oxidative C?N Coupling
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The electrochemical synthesis of N, N’-disubstituted benzimidazolones from ureas through an intramolecular anodic dehydrogenative N?H/C?H coupling has been developed. The reaction undergoes under the undivided electrolysis conditions and obviates the need for any catalysts and chemical oxidants. (Figure presented.).
- Li, Jiang-Sheng,Yang, Pan-Pan,Xie, Xin-Yun,Jiang, Si,Tao, Li,Li, Zhi-Wei,Lu, Cui-Hong,Liu, Wei-Dong
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supporting information
p. 1977 - 1981
(2020/04/20)
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- Bidentate geometry-constrained iminopyridyl nickel-catalyzed synthesis of amines or imines via borrowing hydrogen or dehydrogenative condensation
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The efficient Ni-catalyzed N-alkylation of various anilines with alcohols via borrowing hydrogen is reported using a bidentate geometry-constrained iminopyridyl nickel complex as the catalyst. Substituted benzylic alcohols and short/long chain aliphatic alcohols could be applied as the alkylation sources to couple with aromatic and heteroaromatic amines to give a diverse set of N-alkylation outcomes in moderate to excellent yields. The nickel catalytic system was also suitable for aliphatic amines, selectively delivering the corresponding imines via an acceptorless dehydrogenative condensation strategy.
- Jiang, Yong,Hu, Miao,Sun, Nan,Hu, Baoxiang,Shen, Zhenlu,Hu, Xinquan,Jin, Liqun
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supporting information
(2020/11/27)
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- Linear Hydroaminoalkylation Products from Alkyl-Substituted Alkenes
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The regioselective conversion of alkyl-substituted alkenes into linear hydroaminoalkylation products represents a strongly desirable synthetic transformation. In particular, such conversions of N-methylamine derivatives are of great scientific interest, because they would give direct access to important amines with unbranched alkyl chains. Herein, we present a new one-pot procedure that includes an initial alkene hydroaminoalkylation with an α-silylated amine substrate and a subsequent protodesilylation reaction that delivers linear hydroaminoalkylation products with high selectivity from simple alkyl-substituted alkenes. For that purpose, new titanium catalysts have been developed, which are able to activate the α-C?H bond of more challenging α-silylated amine substrates. In addition, a direct relationship between the ligand structure of the new catalysts and the obtained regioselectivity is described.
- Warsitz, Michael,Doye, Sven
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supporting information
p. 15121 - 15125
(2020/10/23)
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- A Novel Modified Cross-Coupling of Phenols and Amines Using Dichloroimidazolidinedione (DCID)
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Phenols are considered as an ideal alternative to aryl halides as coupling partners in cross-coupling reactions. In the present work a copper-catalyzed cross-coupling of phenols with various aromatic and aliphatic amines for the synthesis of secondary aryl amines using dichloroimidazolidinedione (DCID) as a new and efficient activating agent has been developed. Substituted phenols were compatible with the standard reaction conditions. The two proposed mechanisms, which are based on the oxidation addition of copper with Ar-OMCID (MCID: Monochloroimidazolidinedione), are also discussed.
- Madankar, Kamelia,Mokhtari, Javad,Mirjafary, Zohreh
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supporting information
p. 1725 - 1729
(2020/09/01)
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- Generalized Chemoselective Transfer Hydrogenation/Hydrodeuteration
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A generalized, simple and efficient transfer hydrogenation of unsaturated bonds has been developed using HBPin and various proton reagents as hydrogen sources. The substrates, including alkenes, alkynes, aromatic heterocycles, aldehydes, ketones, imines, azo, nitro, epoxy and nitrile compounds, are all applied to this catalytic system. Various groups, which cannot survive under the Pd/C/H2 combination, are tolerated. The activity of the reactants was studied and the trends are as follows: styrene'diphenylmethanimine'benzaldehyde'azobenzene'nitrobenzene'quinoline'acetophenone'benzonitrile. Substrates bearing two or more different unsaturated bonds were also investigated and transfer hydrogenation occurred with excellent chemoselectivity. Nano-palladium catalyst in situ generated from Pd(OAc)2 and HBPin extremely improved the TH efficiency. Furthermore, chemoselective anti-Markovnikov hydrodeuteration of terminal aromatic olefins was achieved using D2O and HBPin via in situ HD generation and discrimination. (Figure presented.).
- Wang, Yong,Cao, Xinyi,Zhao, Leyao,Pi, Chao,Ji, Jingfei,Cui, Xiuling,Wu, Yangjie
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supporting information
p. 4119 - 4129
(2020/08/10)
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- Titanium-Catalyzed Hydroaminoalkylation of Ethylene
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The first examples of titanium-catalyzed hydroaminoalkylation reactions of ethylene with secondary amines are presented. The reactions can be achieved with various titanium catalysts and they do not require the use of high pressure equipment. In addition, the first solid-state structure of a titanapyrrolidine that is formed by insertion of an alkene into the Ti?C bond of a titanaaziridine is reported.
- Rosien, Michael,T?ben, Iris,Schmidtmann, Marc,Beckhaus, Rüdiger,Doye, Sven
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supporting information
p. 2138 - 2142
(2020/02/05)
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- Hydrogenation reaction method
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The invention relates to a hydrogenation reaction method, and belongs to the technical field of organic synthesis. The hydrogenation reaction method provided by the invention comprises the following steps: carrying out a hydrogen transfer reaction on a hydrogen acceptor compound, pinacol borane and a catalyst in a solvent in the presence of proton hydrogen, so that the hydrogen acceptor compound is subjected to a hydrogenation reaction; the catalyst is one or more than two of a palladium catalyst, an iridium catalyst and a rhodium catalyst; the hydrogen acceptor compound comprises one or morethan two functional groups of carbon-carbon double bonds, carbon-carbon triple bonds, carbon-oxygen double bonds, carbon-nitrogen double bonds, nitrogen-nitrogen double bonds, nitryl, carbon-nitrogentriple bonds and epoxy. The method is mild in reaction condition, easy to operate, high in yield, short in reaction time, wide in substrate application range, suitable for carbon-carbon double bonds,carbon-carbon triple bonds, carbon-oxygen double bonds, carbon-nitrogen double bonds, nitrogen-nitrogen double bonds, nitryl, carbon-nitrogen triple bonds and epoxy functional groups, good in selectivity and high in reaction specificity.
- -
-
Paragraph 0034; 0101-0104
(2020/05/14)
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- Plasma-Made (Ni0.5Cu0.5)Fe2O4 Nanoparticles for Alcohol Amination under Microwave Heating
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Amine N-alkylation is a process involved in the production of a wide range of chemicals. Here we describe the synthesis of well-defined (Ni0.5Cu0.5)Fe2O4 magnetic nanoparticles by plasma induction, and their successful application to amine N-alkylation using alcohols as coupling agents through a borrowing hydrogen pathway. Plasma induction allows precise morphology and size control over nanoparticle synthesis, while allowing the one-pot production of decagram quantities of material. Up to date, such nanoparticles have never been applied for organic reactions. By coupling high-end characterization techniques with catalytic optimization, we showed that small Cu(0) satellite nanoparticles played an essential role in alcohol oxidation, whereas both Ni and Cu were required for the last step of the reaction. Using elemental mapping, we demonstrated that catalyst deactivation occurred through a leaching/re-deposition mechanism of Cu and Ni. The reactions were conducted under microwave conditions, which exerted a positive effect on catalytic activity. Finally, the catalyst was active at low metal loadings (2 mol%) even on the gram-scale, and affording unprecedented TON for this reaction catalyzed by Ni/Cu bimetallic systems (19).
- Li, Alain You,Dumaresq, Nicolas,Segalla, Andréanne,Braidy, Nadi,Moores, Audrey
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p. 3959 - 3972
(2019/08/12)
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- A Highly Active PN3 Manganese Pincer Complex Performing N-Alkylation of Amines under Mild Conditions
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A highly active Mn(I) catalyst based on a nonsymmetric PN3-ligand scaffold for the N-alkylation of amines with alcohols utilizing the borrowing hydrogen methodology is reported. A broad range of anilines and the more challenging aliphatic amines were alkylated with primary and secondary alcohols. Moreover, the combination of low catalyst loadings and mild reaction conditions provides high efficiency for this atom-economic transformation.
- Homberg, Leonard,Roller, Alexander,Hultzsch, Kai C.
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supporting information
(2019/05/07)
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- Colloidal and Nanosized Catalysts in Organic Synthesis: XXIII. Reductive Amination of Carbonyl Compounds Catalyzed by Nickel Nanoparticles in a Plug-Flow Reactor
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Reductive amination of aldehydes and ketones with primary and secondary amines under catalysis with nickel nanoparticles supported on zeolite X, MgO, or activated carbon in the gas phase or in the gas-liquid system in a plug-flow reactor proceeds at atmospheric pressure of hydrogen with the formation of secondary or tertiary amines in high yield.
- Mokhov, V. M.,Nebykov, D. N.,Paputina, A. N.,Popov, Yu. V.,Shishkin, E. V.
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p. 2333 - 2340
(2020/02/25)
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- Aluminosilicates with Different Porous Structures in the Synthesis of 2-Ethyl-3-Methylquinoline
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Abstract: The catalytic properties of microporous zeolites of different structural types (FAU, BEA, MOR, and MFI), a micro–meso–macroporous zeolite (H-Ymmm), and an ASM mesoporous aluminosilicate in the reaction of aniline with propionic aldehyde have been studied. It has been found that the reaction proceeds with a high conversion of aniline (90–99% over zeolites and 71% over an ASM aluminosilicate) to form two main products, namely, 2-ethyl-3-methylquinoline (2) and 2-ethyl-3-methyl-N-phenyl-1,2,3,4-tetrahydroquinoline-4-amine (3). The most selective catalysts for the synthesis of quinoline 2 are H-Y (up to 64%) and H-Ymmm (59%) zeolites and the ASM aluminosilicate (50%). It has been shown that an increase in the quinoline 2 selectivity is promoted by an increase in the catalyst acidity, in the reaction temperature to 160°C, in the catalyst concentration to 20 wt %, and in the aniline : aldehyde molar ratio to 1 : 2.
- Grigor’eva,Kostyleva,Gataulin,Khazipova,Narender, Nama,Kutepov
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p. 719 - 725
(2019/08/13)
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- Mesoporous Aluminosilicates in the Synthesis of N-Heterocyclic Compounds
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Abstract: The catalytic properties of samples of amorphous mesoporous aluminosilicate ASM with different Si/Al molar ratios (40, 80, 160) were studied in the synthesis of practically important pyridines (by the interaction of С2–С5 alcohols with formaldehyde and ammonia, cyclocondensation of acetaldehyde and propionic aldehyde with ammonia), dialkylquinolines and alkyltetrahydroquinolines (by reaction of aniline with C3, C4 aldehydes) and alkyldihydroquinolines (by interaction of aniline with ketones, acetone and acetophenone). It is found that mesoporous aluminosilicate ASM sample with a molar ratio of Si/Al = 40, which has the highest acidity among the studied samples, exhibits the highest activity and selectivity in these reactions.
- Agliullin, M. R.,Bikbaeva, V. R.,Bubennov, S. V.,Filippova, N. A.,Gataulin, A. R.,Grigor’eva, N. G.,Kostyleva, S. A.,Kutepov, B. I.,Narender, Nama
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p. 733 - 743
(2020/02/25)
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- Alkylation of Aromatic Amines with Trialkyl Amines Catalyzed by a Defined Iridium Complex with a 2-Hydroxypyridylmethylene Fragment
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Six Cp?Ir complexes containing NN-bitentate chelate ligands [Cp?IrCl(C5H4CH2C5H3OH)][Cl] (1), [Cp?IrCl(C5H4CH2C5H3O)] (2), [Cp?IrCl(C5H4C5H3OH)] [Cl] (3), [Cp?IrCl(C5H4CH2C5H4)][Cl] (4), [Cp?IrCl(CH3OC5H3CH2C5H3OCH3)][Cl] (5), and [Cp?IrCl(CH3OC5H3CH2C5H3OH)][Cl] (6) were synthesized and characterized. Complex 1 could be transformed to 2 when reacted with NaOtBu or NEt3 via -OH deprotonation. These six complexes were tested as catalysts for mono-N-alkylation of amines with trialkyl amines, and complex 1 exhibited highest activity. The coupling reactions proceed under air condition, with 1 mol % catalyst loading without extra base in methanol at 120 °C and can be further accelerated by adding NR3·HCl.
- Deng, Danfeng,Hu, Bowen,Zhang, Ziyu,Mo, Shengkai,Yang, Min,Chen, Dafa
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p. 2218 - 2226
(2019/05/21)
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- Bench-Stable Cobalt Pre-Catalysts for Mild Hydrosilative Reduction of Tertiary Amides to Amines and Beyond
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The readily synthesized and bench-stable cobalt dichloride complex (dpephos)CoCl2 is employed as a pre-catalyst for a diversity of silane additions to unsaturated organic molecules, including the normally challenging reduction of amides to amines. With regard to hydrosilative reduction of amides even more effective and activator free catalytic systems can be generated from the bench-stable, commercially available Co(acac)2 and Co(OAc)2 with dpephos and PPh3 ligands. These systems operate under mild conditions (100 °C), with many examples of room temperature transformations, presenting a first example of mild cobalt-catalyzed hydrosilylation of amides.
- Nurseiit, Alibek,Janabel, Jaysan,Gudun, Kristina A.,Kassymbek, Aishabibi,Segizbayev, Medet,Seilkhanov, Tulegen M.,Khalimon, Andrey Y.
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p. 790 - 798
(2019/01/09)
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- Highly Selective, Efficient Deoxygenative Hydrogenation of Amides Catalyzed by a Manganese Pincer Complex via Metal-Ligand Cooperation
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Deoxygenative hydrogenation of amides to amines homogeneously catalyzed by a complex of an Earth-abundant metal is presented. This manganese-catalyzed reaction features high efficiency and selectivity. A plausible reaction mechanism, involving metal-ligand cooperation of the manganese pincer complex, is proposed based on NMR studies and relevant stoichiometric reactions.
- Zou, You-Quan,Chakraborty, Subrata,Nerush, Alexander,Oren, Dror,Diskin-Posner, Yael,Ben-David, Yehoshoa,Milstein, David
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p. 8014 - 8019
(2018/09/06)
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- Hydrogenolysis of Amide Acetals and Iminium Esters
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Amide acetals and iminium esters were hydrogenated into amines under very mild reaction conditions over common hydrogenation catalysts. This finding provides a new strategy for the selective reduction of amides. The synthetic utility of this approach was demonstrated by the selective reduction of amides bearing ester and nitrile groups.
- Kadyrov, Renat
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p. 170 - 172
(2017/12/26)
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- Method for preparing secondary aromatic amine or tertiary aromatic amine by conducting amination on aryl halide or alkyl halide
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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.
- -
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Paragraph 0029-0035; 0160; 0116; 0117; 0162
(2019/01/14)
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- Colloidal and Nanosized Catalysts in Organic Synthesis: XX. Continuous Hydrogenation of Imines and Enamines Catalyzed by Nickel Nanoparticles
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Nickel nanoparticles on the BAU-A active carbon or NaX zeolite catalyze hydrogenation of imines and enamines in a flow reactor in a gas phase or in a gas–liquid–solid catalyst system. The process occurs at atmospheric pressure of hydrogen and gives secondary or tertiary amines in a high yield.
- Popov, Yu. V.,Mokhov,Latyshova,Nebykov,Panov,Davydova
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p. 2035 - 2038
(2018/12/11)
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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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- Fe(CrO2)2-catalyzed, photoactivated oxidative one-pot tandem synthesis of substituted quinolines from primary alcohols and arylamines
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[Figure not available: see fulltext.] A one-pot tandem synthesis of substituted quinolines involving selective catalytic oxidation of primary alcohols to the corresponding aldehydes and their subsequent condensation with arylamines has been developed. Fe(CrO2)2 has been used as a catalyst, and oxidation has been performed with aqueous H2O2. To accelerate the catalytic oxidation of alcohols, photoactivation method has been applied.
- Makhmutov, Aynur R.,Mustafin, Akhat G.,Usmanov, Salavat M.
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p. 369 - 374
(2018/05/28)
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- Transfer Hydrogenation of Alkenes Using Ethanol Catalyzed by a NCP Pincer Iridium Complex: Scope and Mechanism
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The first general catalytic approach to effecting transfer hydrogenation (TH) of unactivated alkenes using ethanol as the hydrogen source is described. A new NCP-type pincer iridium complex (BQ-NCOP)IrHCl containing a rigid benzoquinoline backbone has been developed for efficient, mild TH of unactivated C-C multiple bonds with ethanol, forming ethyl acetate as the sole byproduct. A wide variety of alkenes, including multisubstituted alkyl alkenes, aryl alkenes, and heteroatom-substituted alkenes, as well as O- or N-containing heteroarenes and internal alkynes, are suitable substrates. Importantly, the (BQ-NCOP)Ir/EtOH system exhibits high chemoselectivity for alkene hydrogenation in the presence of reactive functional groups, such as ketones and carboxylic acids. Furthermore, the reaction with C2D5OD provides a convenient route to deuterium-labeled compounds. Detailed kinetic and mechanistic studies have revealed that monosubstituted alkenes (e.g., 1-octene, styrene) and multisubstituted alkenes (e.g., cyclooctene (COE)) exhibit fundamental mechanistic difference. The OH group of ethanol displays a normal kinetic isotope effect (KIE) in the reaction of styrene, but a substantial inverse KIE in the case of COE. The catalysis of styrene or 1-octene with relatively strong binding affinity to the Ir(I) center has (BQ-NCOP)IrI(alkene) adduct as an off-cycle catalyst resting state, and the rate law shows a positive order in EtOH, inverse first-order in styrene, and first-order in the catalyst. In contrast, the catalysis of COE has an off-cycle catalyst resting state of (BQ-NCOP)IrIII(H)[O(Et)···HO(Et)···HOEt] that features a six-membered iridacycle consisting of two hydrogen-bonds between one EtO ligand and two EtOH molecules, one of which is coordinated to the Ir(III) center. The rate law shows a negative order in EtOH, zeroth-order in COE, and first-order in the catalyst. The observed inverse KIE corresponds to an inverse equilibrium isotope effect for the pre-equilibrium formation of (BQ-NCOP)IrIII(H)(OEt) from the catalyst resting state via ethanol dissociation. Regardless of the substrate, ethanol dehydrogenation is the slow segment of the catalytic cycle, while alkene hydrogenation occurs readily following the rate-determining step, that is, β-hydride elimination of (BQ-NCOP)Ir(H)(OEt) to form (BQ-NCOP)Ir(H)2 and acetaldehyde. The latter is effectively converted to innocent ethyl acetate under the catalytic conditions, thus avoiding the catalyst poisoning via iridium-mediated decarbonylation of acetaldehyde.
- Wang, Yulei,Huang, Zhidao,Leng, Xuebing,Zhu, Huping,Liu, Guixia,Huang, Zheng
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supporting information
p. 4417 - 4429
(2018/04/05)
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- Nano CoCuFe2O4-catalyzed coupling reaction of arylboronic acid with amines and thiols: An atom-economic and ligand-free route to access unsymmetrical amines and sulfides
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An efficient protocol was developed for the nano CoCuFe2O4-catalyzed C-N and C-S bond formation. By this catalytic system, both amine and sulfide-based structural motifs were formed efficiently in aryl halide-free route. The amination reaction of phenyl boronic acid with various types of amines was conducted under ligand-free conditions, in ethanol as a green solvent at 60°C. Unsymmetrical diaryl/aryl alkyl sulfide synthesis via the coupling reaction of arylboronic acids with thiols was also conducted. The nano cobalt-copper ferrite was used as a heterogenous efficient, inexpensive, magnetically separable and recyclable catalyst that can be used for several cycles.
- Moghaddam, Firouz Matloubi,Pourkaveh, Raheleh,Gholamtajari, Milad
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- Amphipathic monolith-supported palladium catalysts for chemoselective hydrogenation and cross-coupling reactions
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A palladium catalyst immobilized on an amphipathic and monolithic polystyrene-divinylbenzene polymer bearing strongly acidic cation exchange functions (sulfonic acid moieties) (Pd/CM) was developed. It was used as a catalyst for hydrogenation and ligand-free cross-coupling reactions, such as the Suzuki-Miyaura, Mizoroki-Heck, and copper- and amine-free Sonogashira-type reactions, together with a palladium catalyst supported on monolithic polymer (Pd/AM) bearing basic anion exchange functions (ammonium salt moieties), which has been in practical use for the decomposition of hydrogen peroxide produced as a byproduct during the manufacture of ultrapure water. While the Pd/CM was highly active as a catalyst for the hydrogenation and a variety of reducible functional groups could be reduced, the use of Pd/AM led to a unique chemoselective hydrogenation. Aromatic carbonyl groups were tolerant under the Pd/AM-catalyzed hydrogenation conditions, although benzyl esters, benzyl ethers, and N-Cbz groups could be smoothly hydrocracked. The cross-coupling reactions readily proceeded using either catalyst. The palladium leaching from the Pd/CM into the reaction media was never observed during the Sonogashira-type reaction, which was hardly achieved by other palladium-supported heterogeneous catalysts due to the good affinity of the palladium species with alkynes.
- Monguchi, Yasunari,Wakayama, Fumika,Ueda, Shun,Ito, Ryo,Takada, Hitoshi,Inoue, Hiroshi,Nakamura, Akira,Sawama, Yoshinari,Sajiki, Hironao
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p. 1833 - 1840
(2017/01/21)
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- Development of a Unique Heterogeneous Palladium Catalyst for the Suzuki–Miyaura Reaction using (Hetero)aryl Chlorides and Chemoselective Hydrogenation
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A unique heterogeneous palladium catalyst (7% Pd/WA30) supported on an anion exchange resin, which contains N,N-dimethylaminoalkyl functionalities on the polymer backbone, was developed. 7% Pd/WA30 could smoothly catalyze Suzuki–Miyaura reactions of even less reactive heteroaryl chlorides and heteroarylboronic acids to afford various (hetero)biaryls due to the electron-donating effect of the tert-amines on WA30 to Pd species. It was also applicable as a chemoselective hydrogenation catalyst, showing inactivity for the hydrogenolysis of tert-butyldimethylsilyl (TBS) ethers, alkyl benzyl ethers, and benzyl alcohols. The tert-amines on WA30 acted as moderate catalyst poisons for Pd, resulting in chemoselective hydrogenation. 7% Pd/WA30 was reused for at least five times without any loss of the hydrogenation catalytic activity. (Figure presented.).
- Ichikawa, Tomohiro,Netsu, Moeko,Mizuno, Masahiro,Mizusaki, Tomoteru,Takagi, Yukio,Sawama, Yoshinari,Monguchi, Yasunari,Sajiki, Hironao
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supporting information
p. 2269 - 2279
(2017/07/07)
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- Direct Reductive Amination of Aldehydes via Environmentally Benign Bentonite-Gold Nanohybrid Catalysis
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An efficient, green and reliable method for the direct reductive amination of aldehydes was developed using an environmentally benign bentonite-gold nanohybrid catalyst. Use of this heterogeneous catalyst affords a variety of secondary amines in excellent yield under ambient reaction conditions in the presence of phenyldimethylsilane as mild hydride donor. The catalyst is recyclable, selective and is well applicable for the gram-scale preparation of secondary amines. (Figure presented.).
- Maya,Poulose, Susanna,John, Jubi,Luxmi Varma
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p. 1177 - 1184
(2017/04/11)
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- REDUCTIVE ALKYLATION OF AMINES WITH ORTHOCARBOXYLIC ACID ESTERS
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The present invention relates to a process for the N-alkylation of amines by reacting an amine with an orthocarboxylic acid ester and with hydrogen in the presence of a hydrogenation catalyst.
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-
Page/Page column 9; 10
(2017/12/27)
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- A new route to α,ω-diamines from hydrogenation of dicarboxylic acids and their derivatives in the presence of amines
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A new and selective route for the synthesis of polymer precursors, primary diamines or N-substituted diamines, from dicarboxylic acids, diesters, diamides and diols using a Ru/triphos catalyst is reported. Excellent conversions and yields are obtained under optimised reaction conditions. The reactions worked very well using 1,4-dioxane as solvent, but the greener solvent, 2-methyl tetrahydrofuran, also gave very similar results. This method provides a potential route to converting waste biomass to value added materials. The reaction is proposed to go through both amide and aldehyde pathways.
- Shi, Yiping,Kamer, Paul C. J.,Cole-Hamilton, David J.
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supporting information
p. 5460 - 5466
(2017/11/22)
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- Heterogeneous catalytic synthesis of quinoline compounds from aniline and C1-C4 alcohols over zeolite-based catalysts
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The synthesis of quinolines from aniline and a C1-C4 alcohol was conducted under gas-phase reaction conditions over a series of zeolite-based catalysts. The texture and acid properties of catalysts were characterized by XRD, FT-IR, BET and NH3-TPD techniques. It was found that the total yield of quinolines was positively related to the relative content of Lewis acid sites of the catalyst. Among others, the ZnCl2/Ni-USY-acid catalyst possessed the best performance. Over this catalyst, the reactions of aniline and most of the alcohols provided a 42.3-79.7% total yield of quinolones under mild conditions, however, those of aniline and methanol, ethanol and iso-propanol predominantly led to N-alkylanilines. Furthermore, the reaction pathways for synthesizing quinolines via aniline reacting with polyhydric alcohols or monohydric alcohols was proposed in our work.
- Huang, Chen,Li, An,Chao, Zi-Sheng
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p. 48275 - 48285
(2017/10/31)
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- Synthesis of quinolines from aniline and propanol over modified USY zeolite: Catalytic performance and mechanism evaluated by: In situ Fourier transform infrared spectroscopy
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The reaction of aniline and propanol to quinolines was conducted in a fixed-bed flow-type reactor, using a series of modified USY zeolite catalysts. The structural, textural and acidic properties of the catalyst were characterized by XRD, N2-physisorption, 27Al MAS NMR, NH3-TPD and pyridine-FTIR, while the mechanism for the reaction of aniline and propanol was investigated by in situ FTIR. It was identified that the reaction of aniline and propanol generated predominantly quinolines, including 2-ethyl-3-methylquinoline and other alkyl quinoline, N-alkyl aniline and other byproducts. Among others, the ZnCl2/Ni-USY catalyst exhibited the best performance, providing a 96.4% conversion of aniline and a 78.3% total yield of quinolines with 81.2% total selectivity to quinolines and 60.1% selectivity to 2-ethyl-3-methylquinoline at 683 K. This was attributed to the larger concentration ratio of Lewis acid sites to Bronsted acid sites over the ZnCl2/Ni-USY catalyst, relative to other catalysts. There were predominantly two possible routes for the formation of quinolines, which required predominantly Lewis acid sites and Bronsted acid sites, respectively. In both the routes, N-phenylpropan-1-imine was proposed as the key intermediate. Relative to that based on Bronsted acid sites, the route based on Lewis acid sites appeared to contribute much more in the generation of quinolines from the reaction of aniline and propanol.
- Huang, Chen,Li, An,Li, Li-Jun,Chao, Zi-Sheng
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p. 24950 - 24962
(2017/07/10)
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- Convenient N-Alkylation of amines using an effective magnetically separable supported ionic liquid containing an anionic polyoxometalate
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Abstract: An effective synthesis of anion-exchanged supported ionic liquid using magnetically separable nanoparticles and its catalytic effect on N-alkylation reactions is described. Anionic polyoxometalate derivative was used in the anion-exchange step in catalyst design. The catalytic system can be easily separated from the reaction mixture with external magnetic field and recycled in subsequent reactions. In order to evaluate catalyst repeatability, N-alkylation of some more amines such as Aniline, 4-aminobenzenesulfonamide, 4-methoxyaniline, 2-aminopyrimidin and 4,5,6,7-tetrahydrobenzo[d]thiazole-2,6-diamine in the presence of recoverable catalyst was successfully examined in this article. In addition, pramipexole dihydrochloride as an active pharmaceutical ingredient was successfully synthesized using the catalytic system. The structure of catalyst was determined by infrared spectroscopy, X-ray powder diffraction, and scanning electron microscope techniques. The structure of organic products was determined by 1H NMR, 13C NMR, infrared and Mass spectroscopy. Graphical Abstract: [Figure not available: see fulltext.]
- Ghasemi, Mohammad Hadi,Kowsari, Elaheh
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p. 1957 - 1968
(2017/02/15)
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- Deoxygenative Hydrogenation of Amides Catalyzed by a Well-Defined Iridium Pincer Complex
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The iridium-catalyzed highly chemoselective hydrogenation of amides to amines has been developed. Using a well-defined iridium catalyst bearing a P(O)C(O)P pincer ligand combined with B(C6F5)3, the C-O cleavage products are formed under mild reaction conditions. The reaction provides a new method for the preparation of amines from amides in good yield with high selectivity.
- Yuan, Ming-Lei,Xie, Jian-Hua,Zhu, Shou-Fei,Zhou, Qi-Lin
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p. 3665 - 3669
(2016/07/06)
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- Catalytic Hydrogenation for the Preparation of Amines from Amide Acetals, Ketene N,O-Acetals or Ester Imides
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The present invention relates to a process for the preparation of amines, comprising the following steps: Reaction of a (i) amide acetal of the general formula (I), or (ii) ketene N,O-acetal of the general formula (II), or (iii) ester imide of the general formula (III) with H2 in the presence of a hydrogenation catalyst, where catalyst and amide acetal or ketene N,O-acetal or ester imide are used in a molar ratio of from 1:10 to 1:100 000 and where a hydrogen pressure of from 0.1 bar to 200 bar is established and where a temperature in the range of from 0° C. to 250° C. is established.
- -
-
Paragraph 0153; 0154
(2016/10/04)
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- Orthogonal Discrimination among Functional Groups in Ullmann-Type C-O and C-N Couplings
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The copper-catalyzed arylation of nucleophiles has been established as an efficient methodology for the formation of C-C and C-heteroatom bonds. Considering the advances during the last two decades, the ligand choice plays a key role in such transformations and can strongly influence the catalytic efficiency. The applicability of these Ullmann-type coupling reactions regarding the orthogonal selectivity of different functional groups constitutes a challenging subject for current synthetic strategies. Herein, we report a useful toolkit of Cu-based catalysts for the chemoselective arylation of a wide-range of nucleophiles in competitive reactions using aryl iodides and bromides. We show in this work that the arylation of all kinds of amides can be orthogonal to that of amines (aliphatic or aromatic) and phenol derivatives. This high chemoselectivity can be governed by the use of different ligands, yielding the desired coupling products under mild conditions. The selectivity trends are maintained for electronically biased iodobenzene and bromobenzene electrophiles. Radical clock experiments discard the occurrence of radical-based mechanisms.
- Rovira, Mireia,Soler, Marta,Güell, Imma,Wang, Ming-Zheng,Gómez, Laura,Ribas, Xavi
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supporting information
p. 7315 - 7325
(2016/09/09)
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- Boron Lewis Acid Promoted Ruthenium-Catalyzed Hydrogenation of Amides: An Efficient Approach to Secondary Amines
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The hydrogenation of amides to amines has been developed by using the catalyst [Ru(H)2(CO)(Triphos)] (Triphos=1,1,1-tri(diphenylphosphinomethyl)ethane) and catalytic boron Lewis acids such as B(C6F5)3 or BF3?Et2O as additives. The reaction provides an efficient method for the preparation of secondary amines from amides in good yields with high selectivity.
- Yuan, Ming-Lei,Xie, Jian-Hua,Zhou, Qi-Lin
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p. 3036 - 3040
(2016/10/11)
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- Esters, Including Triglycerides, and Hydrogen as Feedstocks for the Ruthenium-Catalyzed Direct N-Alkylation of Amines
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Triglycerides are used for the direct N-alkylation of amines with molecular hydrogen for the first time. A broad range of interesting and industrially relevant secondary and tertiary amines are obtained in the presence of an in situ formed Ru/Triphos complex. Notably, plant oil can be efficiently applied in this single-step process. Moreover, a variety of other methyl esters can be used as N-alkylation agents in the presence of hydrogen for the synthesis of more advanced building blocks.
- Adam, Rosa,Cabrero-Antonino, Jose R.,Junge, Kathrin,Jackstell, Ralf,Beller, Matthias
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supporting information
p. 11049 - 11053
(2016/10/13)
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- Symbiotic Transition-Metal and Organocatalysis for Catalytic Ambient Amine Oxidation and Alkene Reduction Reactions
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A new oxidation reaction based on two simple catalysts, namely, alloxan and a CuI salt, is highly effective for the aerobic oxidation and oxidative cross-coupling of amines. The reaction is operationally simple, reaction atmospheres enriched in dioxygen are obviated, and neither catalyst component requires prior synthesis. Mechanistic investigations have been performed and point towards a complex reaction manifold with evidence that supports a catalytic cycle that does not proceed through a quinone-imine step. Additionally, this dual catalyst system is efficient to effect diimide-mediated hydrogenation reactions of alkenes and alkynes, a transformation that has not been reported previously in the context of quinone catalyst systems.
- Murray, Alexander T.,King, Rose,Donnelly, Joseph V. G.,Dowley, Myles J. H.,Tuna, Floriana,Sells, Daniel,John, Matthew P.,Carbery, David R.
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p. 510 - 514
(2016/02/20)
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- Unique Chemoselective Hydrogenation using a Palladium Catalyst Immobilized on Ceramic
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A heterogeneous palladium catalyst supported on a ceramic (5 % Pd/ceramic) was developed. The catalyst exhibited a specific chemoselectivity for hydrogenation that has never been achieved by other palladium-catalyzed methods. Either aliphatic or aromatic N-Cbz groups could be deprotected to the corresponding free-amines, while the hydrogenolysis of benzyl esters and ethers did not proceed. Furthermore, aryl chlorides and epoxides were tolerant under the Pd/ceramic-catalyzed hydrogenation conditions. 5 % Pd/ceramic could be reused without any loss of catalyst activity, as no palladium leaching was detected in the reaction media.
- Monguchi, Yasunari,Marumoto, Takahisa,Ichikawa, Tomohiro,Miyake, Yutaka,Nagae, Yoshiyuki,Yoshida, Michiyuki,Oumi, Yasunori,Sawama, Yoshinari,Sajiki, Hironao
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p. 2155 - 2160
(2015/11/24)
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- Direct N-alkylation of aromatic amines using a microflow reactor: Enhancement of selectivity and reactivity
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A simple and highly atom-economical method for the direct N-alkylation of aromatic amines by using a microflow reactor was developed to overcome the problem of over-alkylation. In the developed method, high-yield conversion (up to 100%) was achieved in a relatively short reaction time. The ratio of mono- to di-benzylated products (3.57:1) was higher than that achieved with batch reactions conducted in a 1 L scale flask (0.87:1). The structural features of the microflow reactor meant that short-chain alkyl halides could be converted into products with high reactivity and selectivity under superheating conditions, although their boiling point was much lower than the reaction temperature. This method was successfully applied to the synthesis of a range of secondary amines including an intermediate of indobufen synthesis.
- Choi, Yong-Sung,Kim, Yoon-Jung,Shen, Liu-Lan,Lee, Yong Sup,Jeong, Jin-Hyun
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supporting information
p. 970 - 974
(2015/04/27)
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- One-pot reductive amination of araldehydes by aniline using borohydride with CeCl3·7H2O as catalyst
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A one-pot, two-step reductive amination of araldehydes or acetophenones with anilines using NaBH4as a cheap hydride source and catalysed by CeCl3·7H2O has been achieved in EtOH at room temperature in good yields.
- Zhu, Xun,Zhou, Xiuqin,Zhang, Wei
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p. 390 - 393
(2015/08/18)
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- Photocatalytic secondary amine synthesis from azobenzenes and alcohols on TiO2 loaded with Pd nanoparticles
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Photoirradiation (λ > 300 nm) of TiO2 loaded with Pd nanoparticles (ca. 2 wt%, 5 nm diameter) in water containing alcohols and azobenzene derivatives at room temperature successfully produces the corresponding secondary amines with high yields.
- Selvam, Kaliyamoorthy,Sakamoto, Hirokatsu,Shiraishi, Yasuhiro,Hirai, Takayuki
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p. 2856 - 2860
(2015/04/22)
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- Palladium-catalyzed oxidative carbonylation of aromatic C-H bonds of N -alkylanilines with CO and alcohols for the synthesis of o -aminobenzoates
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A Pd(II)-catalyzed C-H monocarbonylation of N-alkylanilines for the synthesis of o-aminobenzoates has been developed. Various aliphatic alcohols and phenol were tolerated in the reaction to afford the corresponding o-aminobenzoates in good yields under mild balloon pressure of CO.
- Chen, Ming,Ren, Zhi-Hui,Wang, Yao-Yu,Guan, Zheng-Hui
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p. 1258 - 1263
(2015/01/30)
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- Programmed synthesis palladium supported on Fe3O4@C: An efficient and heterogeneous recyclable catalyst for one-pot reductive amination of aldehydes with nitroarenes in aqueous reaction medium
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A highly efficient Pd/Fe3O4@C catalytic system has been developed for direct reductive amination of carbonyl compounds with nitroarenes in aqueous reaction medium. The catalyst was characterized by TEM, XRD, XPS and VSM. It was found that the catalyst showed a high activity for the one-pot direct reductive amination of aldehydes with nitroarenes in the presence of molecular hydrogen at mild temperature. Besides, the catalyst could be recovered in a facile manner from the reaction mixture and recycled six times without obvious loss in activity.
- Zhou, Xingchun,Li, Xinzhe,Jiao, Lixin,Huo, Hongfei,Li, Rong
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p. 1591 - 1599
(2017/05/22)
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