- Synthesis and characterization of substituted (aminomethyl)lithium compounds: The structures of [Li2(CH2NPh2)2(THF)3] and [Li4(CH2NC5H10)4(THF)2]
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(Aminomethyl)lithium compounds LiCH2NRR′ · x THF (NRR′ = NMe2 (1a, x = 0), NPhMe (1b, x = 2), NPh2 (1c, x = 1 ... 1,5), NC5H10 (1d, x = 0, NC5H10 = piperidino), and NC7H14 (1e, NC7H14 = 2,6-dimethylpiperidino)) were prepared by the reaction of Bu3SnCH2NRR′ with BuLi. 1a-d were isolated in solid state and characterized by NMR spectroscopy (1H, 13C, 7Li). 1e was obtained in solution and characterized via reaction with MeOH and with benzophenone to generate MeNC7H14 and Ph2C(OH)CH2NC7H14, respectively. Recrystallization of 1c and 1d from n-hexane/THF gives [Li2(CH2NPh2)2(THF)3] (1c′) and [Li4(CH2NC5H10)4(THF)2] (1d′), respectively, whose structures (X-ray) were determined. The dimeric compound 1c′ forms a central planar four-membered Li2C2 ring. One lithium atom is four-coordinated to two methylene carbon atoms (d(Li-C) = 2.246(9), 2.235(9) A) and two oxygen atoms of THF. Unusually, the second lithium exhibits a nearly planar coordination sphere represented by two methylene carbon atoms (d(Li-C) = 2.17(1) and 2.16(1) A) and by the oxygen atom of the disordered THF molecule. 1d′ is a tetrameric species exhibiting a molecular C2 symmetry. The lithium atoms are arranged in a distorted tetrahedron with methylene carbon atoms occupying each face of the tetrahedron.
- Becke, Frank,Heinemann, Frank W.,Rueffer, Tobias,Wiegeleben, Peter,Boese, Roland,Blaeser, Dieter,Steinborn, Dirk
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Read Online
- THE MECHANISM OF THE HETEROGENEOUS CATALYSIS OF α AND γ-CYCLIC SIX-MEMBERED AMINOKETONES
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On the basis of catalytic deuteration of cyclic α and γ-aminoketones in 1-2N DCl/D2 or H2, in the presence of PtO2, it is assumed that the mechanism of heterogenous catalysis for both classes of compounds is ionic in character, and that the reaction takes place in the electrical double layer at the interface of solid and liquid.As a consequence of the reduction, two deuteriums (or hydrogens if HCl is used) from the reduction medium are introduced into the molecule, the catalyst only facilitating and not participating in the reaction itself.
- Wysocka, Waleria
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Read Online
- Reduction of Amides to Amines with Pinacolborane Catalyzed by Heterogeneous Lanthanum Catalyst La(CH2C6H4NMe2- o)3@SBA-15
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Hydroboration of amides is a useful synthetic strategy to access the corresponding amines. In this contribution, it was found that the supported lanthanum benzyl material La(CH2C6H4NMe2-o)3@SBA-15 was highly active for the hydroboration of primary, secondary, and tertiary amides to amines with pinacolborane. These reactions selectively produced target amines and showed good tolerance for functional groups such as -NO2, -halogen, and -CN, as well as heteroatoms such as S and O. This reduction procedure exhibited the recyclable and reusable property of heterogeneous catalysts and was applicable to gram-scale synthesis. The reaction mechanisms were proposed based on some control experiments and the previous literature. This is the first example of hydroborative reduction of amides to amines mediated by heterogeneous catalysts.
- Guo, Chenjun,Zhang, Fangcao,Yu, Chong,Luo, Yunjie
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supporting information
p. 13122 - 13135
(2021/08/31)
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- Electrochemical Reductive N-Methylation with CO2Enabled by a Molecular Catalyst
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The development of benign methylation reactions utilizing CO2 as a one-carbon building block would enable a more sustainable chemical industry. Electrochemical CO2 reduction has been extensively studied, but its application for reductive methylation reactions remains out of the scope of current electrocatalysis. Here, we report the first electrochemical reductive N-methylation reaction with CO2 and demonstrate its compatibility with amines, hydroxylamines, and hydrazine. Catalyzed by cobalt phthalocyanine molecules supported on carbon nanotubes, the N-methylation reaction proceeds in aqueous media via the chemical condensation of an electrophilic carbon intermediate, proposed to be adsorbed or near-electrode formaldehyde formed from the four-electron reduction of CO2, with nucleophilic nitrogenous reactants and subsequent reduction. By comparing various amines, we discover that the nucleophilicity of the amine reactant is a descriptor for the C-N coupling efficacy. We extend the scope of the reaction to be compatible with cheap and abundant nitro-compounds by developing a cascade reduction process in which CO2 and nitro-compounds are reduced concurrently to yield N-methylamines with high monomethylation selectivity via the overall transfer of 12 electrons and 12 protons.
- Rooney, Conor L.,Wu, Yueshen,Tao, Zixu,Wang, Hailiang
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supporting information
p. 19983 - 19991
(2021/12/01)
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- A Lewis Base Nucleofugality Parameter, NFB, and Its Application in an Analysis of MIDA-Boronate Hydrolysis Kinetics
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The kinetics of quinuclidine displacement of BH3 from a wide range of Lewis base borane adducts have been measured. Parameterization of these rates has enabled the development of a nucleofugality scale (NFB), shown to quantify and predict the leaving group ability of a range of other Lewis bases. Additivity observed across a number of series R′3-nRnX (X = P, N; R′ = aryl, alkyl) has allowed the formulation of related substituent parameters (nfPB, nfAB), providing a means of calculating NFB values for a range of Lewis bases that extends far beyond those experimentally derived. The utility of the nucleofugality parameter is explored by the correlation of the substituent parameter nfPB with the hydrolyses rates of a series of alkyl and aryl MIDA boronates under neutral conditions. This has allowed the identification of MIDA boronates with heteroatoms proximal to the reacting center, showing unusual kinetic lability or stability to hydrolysis.
- García-Domínguez, Andrés,Gonzalez, Jorge A.,Leach, Andrew G.,Lloyd-Jones, Guy C.,Nichol, Gary S.,Taylor, Nicholas P.
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supporting information
(2022/01/04)
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- Germyliumylidene: A Versatile Low Valent Group 14 Catalyst
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Bis-NHC stabilized germyliumylidenes [RGe(NHC)2]+ are typically Lewis basic (LB) in nature, owing to their lone pair and coordination of two NHCs to the vacant p-orbitals of the germanium center. However, they can also show Lewis acidity (LA) via Ge?CNHC σ* orbital. Utilizing this unique electronic feature, we report the first example of bis-NHC-stabilized germyliumylidene [MesTerGe(NHC)2]Cl (1), (MesTer=2,6-(2,4,6-Me3C6H2)2C6H3; NHC= IMe4=1,3,4,5-tetramethylimidazol-2-ylidene) catalyzed reduction of CO2 with amines and arylsilane, which proceeds via its Lewis basic nature. In contrast, the Lewis acid nature of 1 is utilized in the catalyzed hydroboration and cyanosilylation of carbonyls, thus highlighting the versatile ambiphilic nature of bis-NHC stabilized germyliumylidenes.
- Sarkar, Debotra,Dutta, Sayan,Weetman, Catherine,Schubert, Emeric,Koley, Debasis,Inoue, Shigeyoshi
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supporting information
p. 13072 - 13078
(2021/08/09)
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- N-Methylation and Trideuteromethylation of Amines via Magnesium-Catalyzed Reduction of Cyclic and Linear Carbamates
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A new reduction of carbamates to N-methyl amines is presented. The magnesium-catalyzed reduction reaction allows the conversion of cyclic and linear carbamates, including N-Boc protected amines, into the corresponding N-methyl amines and amino alcohols which are of significant interest due to their presence in many biologically active molecules. Furthermore, the reduction can be extended to the formation of N-trideuteromethyl labeled amines.
- Magre, Marc,Szewczyk, Marcin,Rueping, Magnus
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supporting information
p. 3209 - 3214
(2020/04/10)
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- Electroactivated alkylation of amines with alcohols: Via both direct and indirect borrowing hydrogen mechanisms
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A green, efficient N-alkylation of amines with simple alcohols has been achieved in aqueous solution via an electrochemical version of the so-called "borrowing hydrogen methodology". Catalyzed by Ru on activated carbon cloth (Ru/ACC), the reaction works well with methanol, and with primary and secondary alcohols. Alkylation can be accomplished by either of two different electrocatalytic processes: (1) in an undivided cell, alcohol (present in excess) is oxidized at the Ru/ACC anode; the aldehyde or ketone product condenses with the amine; and the resulting imine is reduced at an ACC cathode, combining with protons released by the oxidation. This process consumes stoichiometric quantities of current. (2) In a membrane-divided cell, the current-activated Ru/ACC cathode effects direct C-H activation of the alcohol; the resulting carbonyl species, either free or still surface-adsorbed, condenses with amine to form imine and is reduced as in (1). These alcohol activation processes can alkylate primary and secondary aliphatic amines, as well as ammonia itself at 25-70 °C and ambient pressure.
- Appiagyei, Benjamin,Bhatia, Souful,Keeney, Gabriela L.,Dolmetsch, Troy,Jackson, James E.
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supporting information
p. 860 - 869
(2020/02/21)
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- Powering Artificial Enzymatic Cascades with Electrical Energy
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We have developed a scalable platform that employs electrolysis for an in vitro synthetic enzymatic cascade in a continuous flow reactor. Both H2 and O2 were produced by electrolysis and transferred through a gas-permeable membrane into the flow system. The membrane enabled the separation of the electrolyte from the biocatalysts in the flow system, where H2 and O2 served as electron mediators for the biocatalysts. We demonstrate the production of methylated N-heterocycles from diamines with up to 99 percent product formation as well as excellent regioselective labeling with stable isotopes. Our platform can be applied for a broad panel of oxidoreductases to exploit electrical energy for the synthesis of fine chemicals.
- Al-Shameri, Ammar,Apfel, Ulf-Peter,Lauterbach, Lars,Nestl, Bettina M.,Petrich, Marie-Christine,junge Puring, Kai
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supporting information
p. 10929 - 10933
(2020/05/04)
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- N-Heterocyclic Carbene-Stabilized Germa-acylium Ion: Reactivity and Utility in Catalytic CO2Functionalizations
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The first acceptor-free heavier germanium analogue of an acylium ion, [RGe(O)(NHC)2]X (R = MesTer = 2,6-(2,4,6-Me3C6H2)2C6H3; NHC = IMe4 = 1,3,4,5-tetramethylimidazol-2-ylidene; X = (Cl or BArF = {(3,5-(CF3)2C6H5)4B}), was isolated by reacting [RGe(NHC)2]X with N2O. Conversion of the germa-acylium ion to the first solely donor-stabilized germanium ester [(NHC)RGe(O)(OSiPh3)] and corresponding heavier analogues ([RGe(S)(NHC)2]X and [RGe(Se)(NHC)2]X) demonstrated its classical acylium-like behavior. The polarized terminal GeO bond in the germa-acylium ion was utilized to activate CO2 and silane, with the former found to be an example of reversible activation of CO2, thus mimicking the behavior of transition metal oxides. Furthermore, its transition-metal-like nature is demonstrated as it was found to be an active catalyst in both CO2 hydrosilylation and reductive N-functionalization of amines using CO2 as the C1 source. Mechanistic studies were undertaken both experimentally and computationally, which revealed that the reaction proceeds via an N-heterocyclic carbene (NHC) siloxygermylene [(NHC)RGe(OSiHPh2)].
- Sarkar, Debotra,Weetman, Catherine,Dutta, Sayan,Schubert, Emeric,Jandl, Christian,Koley, Debasis,Inoue, Shigeyoshi
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supporting information
p. 15403 - 15411
(2020/10/20)
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- Method for synthesizing methyl piperidine through 1- supported metal catalysis (by machine translation)
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The invention provides a supported metal-catalyzed synthesis method of methyl 1 - piperidine through a supported, metal, wherein the supported metal is, 1,5 - used as catalyst stanediol and methylamine as H a raw material (I) in the following, formula (I). 2 The supported metal, catalyst comprises 230-330 °C, a carrier and 2-4Mpa an active 1-8h, component 1 - wherein. the supported metal catalyst comprises a carrier and an active component: wherein the supported Cu, Ni, Pd/Ru, metal catalyst comprises Cu a Ni carrier and an active component, wherein 3-15%, the Cu total Ni supported amount of 1:1;Pd/Ru the active component (s) 0-1%; and the mass Al ratio (mass ratio) of the active component (s) to the mass of the carrier (s) is in the range. 2 O3 , SiO2 Alternatively, the ZSM - 5. present invention catalyzes the preparation of 1 - a production, 1,5 - route with an 100%,1 - actual application value by a 93%, one-pot process for the catalytic preparation of the conversion rate of methyl.piperidine-pentanediol to methyl piperidine. (by machine translation)
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Paragraph 0014-0021
(2020/01/25)
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- Selective synthesis of formamides, 1,2-bis(N-heterocyclic)ethanes and methylamines from cyclic amines and CO2/H2 catalyzed by an ionic liquid-Pd/C system
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The reduction of CO2 with amines and H2 generally produces N-formylated or N-methylated compounds over different catalysts. Herein, we report the selective synthesis of formamides, 1,2-bis(N-heterocyclic)ethanes, and methylamines, which is achieved over an ionic liquid (IL, e.g., 1-butyl-3-methylimidazolium tetrafluoroborate, [BMIm][BF4])-Pd/C catalytic system. By simply varying the reaction temperature, formamides and methylamines can be selectively produced, respectively, in high yields. Interestingly, 1,2-bis(N-heterocyclic)ethanes can also be obtained via the McMurry reaction of the formed formamide coupled with subsequent hydrogenation. It was found that [BMIm][BF4] can react with formamide to form a [BMIm]+-formamide adduct; thus combined with Pd/C it can catalyze McMurry coupling of formamide in the presence of H2 to afford 1,2-bis(N-heterocyclic)ethane. Moreover, Pd/C-[BMIm][BF4] can further catalyze the hydrogenolysis of 1,2-bis(N-heterocyclic)ethane to access methylamine. [BMIm][BF4]-Pd/C was tolerant to a wide substrate scope, giving the corresponding formamides, 1,2-bis(N-heterocyclic)ethanes or methylamines in moderate to high yields. This work develops a new route to produce N-methylamine and opens the way to produce 1,2-bis(N-heterocyclic)ethane from cyclic amine as well.
- Li, Ruipeng,Zhao, Yanfei,Wang, Huan,Xiang, Junfeng,Wu, Yunyan,Yu, Bo,Han, Buxing,Liu, Zhimin
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p. 9822 - 9828
(2019/11/11)
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- Mn-Catalyzed Selective Double and Mono-N-Formylation and N-Methylation of Amines by using CO2
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Functionalization of amines by using CO2 is of fundamental importance considering the abundance of amines and CO2. In this context, the catalytic formylation and methylation of amines represent convenient and successful protocols for selective CO2 utilization as a C1 building block. This study represents the first example of selective catalytic double N-formylation of aryl amines by using a dinuclear Mn complex in the presence of phenylsilane. This robust system also allows for selective formylation and methylation of amines under a range of conditions.
- Huang, Zijun,Jiang, Xiaolin,Zhou, Shaofang,Yang, Peiju,Du, Chen-Xia,Li, Yuehui
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p. 3054 - 3059
(2019/04/10)
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- Unexpected Macrocyclic Multinuclear Zinc and Nickel Complexes that Function as Multitasking Catalysts for CO2 Fixations
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Unique self-assembled macrocyclic multinuclear ZnII and NiII complexes with binaphthyl-bipyridyl ligands (L) were synthesized. X-ray analysis revealed that these complexes consisted of an outer ring (Zn3L3 or Ni3L3) and an inner core (Zn2 or Ni). In the ZnII complex, the inner Zn2 part rotated rapidly inside the outer ring in solution on an NMR timescale. These complexes exhibited dual catalytic activities for CO2 fixations: synthesis of cyclic carbonates from epoxides and CO2 and temperature-switched N-formylation/N-methylation of amines with CO2 and hydrosilane.
- Takaishi, Kazuto,Nath, Bikash Dev,Yamada, Yuya,Kosugi, Hiroyasu,Ema, Tadashi
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supporting information
p. 9984 - 9988
(2019/06/24)
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- Commercial Pd/C-Catalyzed N-Methylation of Nitroarenes and Amines Using Methanol as Both C1 and H2 Source
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Herein, we report commercially available carbon-supported-palladium (Pd/C)-catalyzed N-methylation of nitroarenes and amines using MeOH as both a C1 and a H2 source. This transformation proceeds with high atom-economy and in an environmentally friendly way via borrowing hydrogen mechanism. A total of >30 structurally diverse N-methylamines, including bioactive compounds, were selectively synthesized with isolated yields of up to 95%. Furthermore, selective N-methylation and deuteration of nimesulide, a nonsteroidal anti-inflammatory drug, were realized through the late-stage functionalization.
- Goyal, Vishakha,Gahtori, Jyoti,Narani, Anand,Gupta, Piyush,Bordoloi, Ankur,Natte, Kishore
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p. 15389 - 15398
(2019/12/04)
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- Selective formylation or methylation of amines using carbon dioxide catalysed by a rhodium perimidine-based NHC complex
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Carbon dioxide can play a vital role as a sustainable feedstock for chemical synthesis. To be viable, the employed protocol should be as mild as possible. Herein we report a methodology to incorporate CO2 into primary, secondary, aromatic or alkyl amines catalysed by a Rh(i) complex bearing a perimidine-based NHC/phosphine pincer ligand. The periminide-based ligand belongs to a class of 6-membered NHC ligand accessed through chelate-assisted double C-H activation. N-Formylation and -methylation of amines were performed using a balloon of CO2, and phenylsilane as the reducing agent. Product selectivity between formylated and methylated products was tuned by changing the solvent, reaction temperature and the quantity of phenylsilane used. Medium to excellent conversions, as well as tolerance to a range of functional groups, were achieved. Stoichiometric reactions with reactants employed in catalysis and time course studies suggested that formylation and methylation reactions of interest begin with hydrosilylation of CO2 followed by reaction with amine substrates.
- Lam, Raphael H.,McQueen, Caitlin M. A.,Pernik, Indrek,McBurney, Roy T.,Hill, Anthony F.,Messerle, Barbara A.
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supporting information
p. 538 - 549
(2019/02/14)
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- Copper catalysis: Ligand-controlled selective: N -methylation or N -formylation of amines with CO2 and phenylsilane
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Cupric subcarbonate (Cu2(OH)2CO3) was found to be effective for the reductive functionalization of CO2 to produce formamides and methylamines with phenylsilane as reductant. Interestingly, N-formylation and N-methylation were switched on/off by subtly choosing the ligand: DPPB (1,4-bis(diphenylphosphino)butane) promoted N-methylation whereas Ph2CyP (diphenylcyclohexylphosphine) favored for N-formylation.
- Li, Xue-Dong,Xia, Shu-Mei,Chen, Kai-Hong,Liu, Xiao-Fang,Li, Hong-Ru,He, Liang-Nian
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supporting information
p. 4853 - 4858
(2018/11/21)
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- Method for preparing formamide and N-methylamines by carrying out selective reduction on carbon dioxide and amines regulated by ligand
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The invention relates to a method for preparing formamide and N-methylamines by carrying out selective reduction on carbon dioxide and amines regulated by a ligand. According to the method, copper salt is used as a catalyst, organic amine or organic phosphorus is used as the ligand, CO2 and a hydrosilane are respectively used as a C1 resource and a reducing agent, and amines are used as a nucleophilic reagent; a reaction is carried out in an organic solvent, the consumption of the catalyst is 1-5mol%, and the consumption of the ligand is 1-20 mol%, the reaction temperature is 20-80 DEG C, theCO2 pressure is 0.1-8.0 MPa, the reaction time is 10-48h, the highest yield of the formamide is up to 98%, and the highest yield of the N-methylamine is up to 95%. The method provided by the inventionhas the advantages that the ligand is used for a regulation method for selective reduction preparation of the formamide and the N-methylamines for the first time; the catalyst is low in price, easy to obtain and simple in composition; the renewable CO2 is used as a raw material, so that the use of the traditional toxic formylation and methylation reagents is avoided; the substrate is wide in application scope and is suitable for a variety of secondary amines.
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Paragraph 0135-0143
(2019/01/14)
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- Manganese-Catalyzed N-Formylation of Amines by Methanol Liberating H2: A Catalytic and Mechanistic Study
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The first example of a base metal (manganese) catalyzed acceptorless dehydrogenative coupling of methanol and amines to form formamides is reported herein. The novel pincer complex (iPr-PNHP)Mn(H)(CO)2 catalyzes the reaction under mild conditions in the absence of any additives, bases, or hydrogen acceptors. Mechanistic insight based on the observation of an intermediate and DFT calculations is also provided.
- Chakraborty, Subrata,Gellrich, Urs,Diskin-Posner, Yael,Leitus, Gregory,Avram, Liat,Milstein, David
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supporting information
p. 4229 - 4233
(2017/04/04)
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- Efficient and Selective Hydrosilylation of Secondary and Tertiary Amides Catalyzed by an Iridium(III) Metallacycle: Development and Mechanistic Investigation
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Readily accessible cationic IrIII metallacycles catalyze efficiently the chemoselective hydrosilylation of tertiary and secondary amides to amines. The catalyst described herein operates at low loadings using inexpensive 1,1,3,3-tetramethyldisiloxane and allows fast reactions with high yields, selectivities, and turnover numbers. A transient iminium intermediate has been observed for the first time by using mass spectrometry, and the activation of the catalyst and the silane reagent have been studied by using DFT calculations. These fundamental insights support the present and future improvements of IrIII metallacycles through proper ligand modifications and enable further broad applications of catalysts based on metallacycles.
- Corre, Yann,Trivelli, Xavier,Capet, Frédéric,Djukic, Jean-Pierre,Agbossou-Niedercorn, Francine,Michon, Christophe
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p. 2009 - 2017
(2017/06/13)
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- Mild Hydrogenation of Amides to Amines over a Platinum-Vanadium Bimetallic Catalyst
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Hydrogenation of amides to amines is an important reaction, but the need for high temperatures and H2 pressures is a problem. Catalysts that are effective under mild reaction conditions, that is, lower than 30 bar H2 and 70 °C, have not yet been reported. Here, the mild hydrogenation of amides was achieved for the first time by using a Pt-V bimetallic catalyst. Amide hydrogenation, at either 1 bar H2 at 70 °C or 5 bar H2 at room temperature was achieved using the bimetallic catalyst. The mild reaction conditions enable highly selective hydrogenation of various amides to the corresponding amines, while inhibiting arene hydrogenation. Catalyst characterization showed that the origin of the catalytic activity for the bimetallic catalyst is the oxophilic V-decorated Pt nanoparticles, which are 2 nm in diameter.
- Mitsudome, Takato,Miyagawa, Kazuya,Maeno, Zen,Mizugaki, Tomoo,Jitsukawa, Koichiro,Yamasaki, Jun,Kitagawa, Yasutaka,Kaneda, Kiyotomi
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supporting information
p. 9381 - 9385
(2017/08/01)
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- Rhenium-Loaded TiO2: A Highly Versatile and Chemoselective Catalyst for the Hydrogenation of Carboxylic Acid Derivatives and the N-Methylation of Amines Using H2 and CO2
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Herein, we report a heterogeneous TiO2-supported Re catalyst (Re/TiO2) that promotes various selective hydrogenation reactions, which includes the hydrogenation of esters to alcohols, the hydrogenation of amides to amines, and the N-methylation of amines, by using H2 and CO2. Initially, Re/TiO2 was evaluated in the context of the selective hydrogenation of 3-phenylpropionic acid methyl ester to afford 3-phenylpropanol (pH2 =5 MPa, =5 MPa, T=180 °C), which revealed a superior performance over other catalysts that we tested in this study. In contrast to other typical heterogeneous catalysts, hydrogenation reactions with Re/TiO2 did not produce dearomatized byproducts. DFT studies suggested that the high selectivity for the formation of alcohols in favor of the hydrogenation of aromatic rings is ascribed to the higher affinity of Re towards the COOCH3 group than to the benzene ring. Moreover, Re/TiO2 showed a wide substrate scope for the hydrogenation reaction (19 examples). Subsequently, this Re/TiO2 catalyst was applied to the hydrogenation of amides, the N-methylation of amines, and the N-alkylation of amines with carboxylic acids or esters.
- Toyao, Takashi,Siddiki,Morita, Yoshitsugu,Kamachi, Takashi,Touchy, Abeda S.,Onodera, Wataru,Kon, Kenichi,Furukawa, Shinya,Ariga, Hiroko,Asakura, Kiyotaka,Yoshizawa, Kazunari,Shimizu, Ken-Ichi
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supporting information
p. 14848 - 14859
(2017/10/27)
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- Method for synthesizing mepiquat chloride original medicine
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The invention discloses a method for synthesizing a mepiquat chloride original medicine. The method comprises the following steps: adding ethanol into a container, adding pyridine for mixing, adding chloromethane after dissolution, and performing heating reaction to obtain N-methylpyridine chloride; adding the N-methylpyridine chloride and a catalyst into a reaction container, introducing hydrogen, performing heating reaction to obtain an N-methylpiperidine hydrochloride system, adding an acid binding agent into the N-methylpiperidine hydrochloride system for neutralization reaction, and performing filtering to obtain N-methylpiperidine; dissolving the N-methylpiperidine in ethanol, and adding chloromethane for heating reaction; evaporating a reaction system to remove the ethanol and the chloromethane to obtain a high-purity mepiquat chloride product. According to the method, the using amount of the acid binding agent is reduced in a production process, and the water cost for production is reduced; in addition, the sustainability is high, the energy consumption is effectively reduced, and the method is a novel production process. Therefore, the method has remarkable economic benefits and social benefits.
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- Photochemical Activation of Tertiary Amines for Applications in Studying Cell Physiology
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Representative tertiary amines were linked to the 8-cyano-7-hydroxyquinolinyl (CyHQ) photoremovable protecting group (PPG) to create photoactivatable forms suitable for use in studying cell physiology. The photoactivation of tamoxifen and 4-hydroxytamoxifen, which can be used to activate Cre recombinase and CRISPR-Cas9 gene editing, demonstrated that highly efficient release of bioactive molecules could be achieved through one- and two-photon excitation (1PE and 2PE). CyHQ-protected anilines underwent a photoaza-Claisen rearrangement instead of releasing amines. Time-resolved spectroscopic studies revealed that photorelease of the tertiary amines was extremely fast, occurring from a singlet excited state of CyHQ on the 70 ps time scale.
- Asad, Naeem,Deodato, Davide,Lan, Xin,Widegren, Magnus B.,Phillips, David Lee,Du, Lili,Dore, Timothy M.
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supporting information
p. 12591 - 12600
(2017/09/23)
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- Carboxylate-promoted reductive functionalization of CO2 with amines and hydrosilanes under mild conditions
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Various oxygen-nucleophiles especially carboxylates, e.g. cesium/tetrabutylammonium carboxylate, were proved to be efficient and selective catalysts for reductive functionalization of CO2 with amines and hydrosilanes to methylamines. Various amines including aromatic and aliphatic, primary and secondary ones were methylated successfully in the presence of diphenylsilane as the reductant under 50 °C and an atmospheric pressure of CO2. Furthermore, a reaction pathway involving CO2 reduction to the C0 species i.e. aminal rather than the formamide as the intermediate was proposed. This protocol represents a transition metal-free and environmentally friendly option for CO2 conversion to useful chemicals via the formation of C-N bonds coupled with six-electron reduction of CO2 to the methanol level under mild conditions.
- Liu, Xiao-Fang,Qiao, Chang,Li, Xiao-Ya,He, Liang-Nian
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supporting information
p. 1726 - 1731
(2017/06/07)
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- Betaine Catalysis for Hierarchical Reduction of CO2 with Amines and Hydrosilane To Form Formamides, Aminals, and Methylamines
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An efficient, sustainable organocatalyst, glycine betaine, was developed for the reductive functionalization of CO2 with amines and diphenylsilane. Methylamines and formamides were obtained in high yield by tuning the CO2 pressure and reaction temperature. Based on identification of the key intermediate, that is, the aminal, an alternative mechanism for methylation involving the C0 silyl acetal and aminal is proposed. Furthermore, reducing the CO2 amount afforded aminals with high yield and selectivity. Therefore, betaine catalysis affords products with a diversified energy content that is, formamides, aminals and methylamines, by hierarchical two-, four- and six-electron reduction, respectively, of CO2 coupled with C?N bond formation.
- Liu, Xiao-Fang,Li, Xiao-Ya,Qiao, Chang,Fu, Hong-Chen,He, Liang-Nian
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supporting information
p. 7425 - 7429
(2017/06/13)
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- Method for selectively preparing N-monomethylamine compound
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The invention discloses a method for selectively preparing an N-monomethylamine compound. The method takes an amine compound, formaldehyde and H2 as reaction raw materials; the raw materials react in a reaction medium in the presence of a compound catalyst at 30 DEG C-180 DEG C for 2h-48h, so as to obtain the N-monomethylamine compound; and the compound catalyst is composed of oxides of at least two of the following metal or oxides of least one of the following metal and at least one metal simple substance: aluminum, copper, nickel, cobalt and iron. According to the method for preparing the N-monomethylamine compound, the conversion ratio and the selectivity of N-monomethylamine are relatively high; the H2 is used as a reducing agent and is clean, cheap and environment-friendly; the catalyst utilized by the method is cheap, simple to prepare and high in catalysis efficiency; and the method has mild preparation and reaction conditions and the catalyst has no corrosiveness, is easy to separate and can be repeatedly used.
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Paragraph 0034-0035
(2017/08/29)
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- Synthetic method of N-methylpiperidine
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The invention provides a synthetic method of N-methylpiperidine. The synthetic method comprises the steps of heating piperidine to 80-100 DEG C, adding paraformaldehyde and potassium dihydrogen phosphite to react, filtering to obtain N-methylpiperidine and a solid, heating and distilling the obtained solid, and collecting distillate, namely N-methylpiperidine, wherein the molar ratio of piperidine to paraformaldehyde to potassium dihydrogen phosphate is 1 to (1-1.2) to (0.5-0.6). N-methylpiperidine prepared through filtration and distillation is high in purity and can be directly utilized without being purified, and the residual solid is potassium dihydrogen phosphate and can be directly recycled to be used as a fertilizer.
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Paragraph 0026-0033
(2018/04/01)
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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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- Copper(II)-Catalyzed Selective Reductive Methylation of Amines with Formic Acid: An Option for Indirect Utilization of CO2
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A copper-catalyzed protocol for reductive methylation of amines and imine with formic acid as a C1 source and phenylsilane as a reductant is reported for the first time, affording the corresponding methylamines in good to excellent yields under mild conditions. This protocol offers an alternative method for indirect utilization of CO2, as formic acid can be readily obtained from hydrogenation of CO2.
- Qiao, Chang,Liu, Xiao-Fang,Liu, Xi,He, Liang-Nian
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supporting information
p. 1490 - 1493
(2017/03/23)
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- Continuous N-alkylation reactions of amino alcohols using γ-Al2O3 and supercritical CO2: Unexpected formation of cyclic ureas and urethanes by reaction with CO2
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The use of γ-Al2O3 as a heterogeneous catalyst in scCO2 has been successfully applied to the amination of alcohols for the synthesis of N-alkylated heterocycles. The optimal reaction conditions (temperature and substrate flow rate) were determined using an automated self-optimising reactor, resulting in moderate to high yields of the target products. Carrying out the reaction in scCO2 was shown to be beneficial, as higher yields were obtained in the presence of CO2 than in its absence. A surprising discovery is that, in addition to cyclic amines, cyclic ureas and urethanes could be synthesised by incorporation of CO2 from the supercritical solvent into the product.
- Streng, Emilia S.,Lee, Darren S.,George, Michael W.,Poliakoff, Martyn
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supporting information
p. 329 - 337
(2017/03/15)
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- METHOD FOR ALKYLATION OF AMINES
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The present invention provides a simple, efficient, and industrially advantageous method for the alkylation of amines. The present invention relates to a production method for N-alkylamines whereby an amine is reacted with an alcohol in the presence of a ruthenium complex represented by general formula (1): RuXY(CO)(L) (wherein X and Y can be the same or different and represent a monovalent anionic ligand, and L represents a tridentate aminodiphosphine ligand).
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Paragraph 0184; 0185
(2016/02/10)
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- Ruthenium-Catalyzed Methylation of Amines with Paraformaldehyde in Water under Mild Conditions
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Methylated amines are highly important for a variety of pharmaceutical and agrochemical applications. Existing routes for their formation result in the production of large amounts of waste or require high reaction temperatures, both of which impact the ecological and economical footprint of the methodologies. Herein, we report the ruthenium-catalyzed reductive methylation of a range of aliphatic amines, using paraformaldehyde as both substrate and hydrogen source, in combination with water. This reaction proceeds under mild aqueous reaction conditions. Additionally the use of a secondary phase for catalyst retention and recycling has been investigated with promising results.
- van der Waals, Dominic,Heim, Leo. E.,Gedig, Christian,Herbrik, Fabian,Vallazza, Simona,Prechtl, Martin H. G.
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p. 2343 - 2347
(2016/10/24)
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- Self-Sufficient Formaldehyde-to-Methanol Conversion by Organometallic Formaldehyde Dismutase Mimic
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The catalytic networks of methylotrophic organisms, featuring redox enzymes for the activation of one-carbon moieties, can serve as great inspiration in the development of novel homogeneously catalyzed pathways for the interconversion of C1molecules at ambient conditions. An imidazolium-tagged arene–ruthenium complex was identified as an effective functional mimic of the bacterial formaldehyde dismutase, which provides a new and highly selective route for the conversion of formaldehyde to methanol in absence of any external reducing agents. Moreover, secondary amines are reductively methylated by the organometallic dismutase mimic in a redox self-sufficient manner with formaldehyde acting both as carbon source and reducing agent.
- van der Waals, Dominic,Heim, Leo E.,Vallazza, Simona,Gedig, Christian,Deska, Jan,Prechtl, Martin H. G.
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p. 11568 - 11573
(2016/08/05)
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- Glycerol as a Building Block for Prochiral Aminoketone, N-Formamide, and N-Methyl Amine Synthesis
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Prochiral aminoketones are key intermediates for the synthesis of optically active amino alcohols, and glycerol is one of the main biomass-based alcohols available in industry. In this work, glycerol was catalytically activated and purposefully converted with amines to generate highly valuable prochiral aminoketones, as well as N-formamides and N-methyl amines, over CuNiAlOx catalyst. The catalyst structure can be anticipated as nano-Ni species on or in CuAlOx via the formation of nano- Cu?Ni alloy particles. This concept may present a novel and valuable methodology for glycerol utilization.
- Dai, Xingchao,Rabeah, Jabor,Yuan, Hangkong,Brückner, Angelika,Cui, Xinjiang,Shi, Feng
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p. 3133 - 3138
(2016/11/29)
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- Method For Preparing Methylated Amines
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The present invention relates to a method for preparing methylated amines using carbon dioxide and to the use of the method for manufacturing vitamins, pharmaceutical products, glues, acrylic fibres and synthetic leathers, pesticides and fertilizers. The invention also relates to a method for manufacturing vitamins, pharmaceutical products, glues, acrylic fibres, synthetic leathers, pesticides and fertilizers, including a step of preparing methylated amines by the method according to the invention. The present invention also relates to a method for preparing marked methylated amines and to the uses thereof.
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Paragraph 0161-0172
(2015/06/10)
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- PROCESS FOR PRODUCING N-METHYL OR N,N-DIMETYL AMINES
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A process for producing N-methyl or N,N-dimethyl amines, which comprises using amine compound, nitro-containing compound or nitrile compound as a starting material, carbon dioxide as a methylating agent and hydrogen gas as a reducing agent, and allowing them to react in a sealed reactor for 6 to 48 h in a reaction medium at a reaction temperature of 80 to 180 ° C. in the presence of a composite catalyst, so as to provide N-methyl or N,N-dimethyl amines. The process of the present invention is simple and under relative mild reaction conditions. By means of the process of the invention, the target products can be prepared at low cost with a high yield. The catalysts used have a high catalytic activity and can be separated from the reaction system simply and reused. Furthermore, the whole process of the present invention is environmental-friendly and facilitates the cycling use of carbon dioxide.
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Paragraph 0059
(2015/02/18)
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- Room temperature N-alkylation of amines with alcohols under UV irradiation catalyzed by Cu-Mo/TiO2
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It is highly desirable to develop efficient heterogeneous photocatalysts for organic reactions. Here, we show the preparation and catalytic performance of a novel TiO2 (P25) supported Cu and Mo photocatalyst (Cu-Mo/TiO2) for N-alkylation of amines with alcohols under UV irradiation at room temperature. A variety of aromatic and aliphatic amines were selectively converted into the corresponding secondary amines or tertiary amines in moderate to excellent yields without the addition of any co-catalysts such as bases and organic ligands. Noteworthy, this catalytic system is feasible in the alkylation of anilines containing halogen substituents with alcohols and the yields of the desired products are up to 95%.
- Zhang, Lina,Zhang, Yan,Deng, Youquan,Shi, Feng
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p. 3226 - 3234
(2015/06/08)
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- Light-promoted N,N-dimethylation of amine and nitro compound with methanol catalyzed by Pd/TiO2 at room temperature
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A series of TiO2 supported nano-Pd catalysts (Pd/TiO2) were prepared and used for the N,N-dimethylation of different amines and nitro compounds with methanol under UV irradiation at room temperature. A wide range of N,N-dimethyl amines were one-pot synthesized with up to 98% by applying aliphatic secondary amines, aromatic primary amines, aliphatic primary amines and aromatic nitro compounds as starting materials. It is noteworthy that up to 90% yield of 4-chloro-N,N-dimethylaniline was obtained by adjusting the Pd loadings on the TiO2 and the dehalogenation reaction was inhibited. Finally, a reaction mechanism is discussed, involving PhN = CH2 and PhNHCH3 as reaction intermediates.
- Zhang, Lina,Zhang, Yan,Deng, Youquan,Shi, Feng
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p. 14514 - 14521
(2015/03/05)
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- Thermal activation of solid-state molybdenum halide clusters with an octahedral cluster framework and their application to catalytic synthesis of 3-methylpyridine from piperidine and methanol
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Solid-state molybdenum halide clusters with an octahedral metal framework MoX2 (or [Mo6X8]X2X4/2) (X= Cl, Br, I) are applied to catalysis. When these clusters are thermally activated in a hydrogen stream above 300°C, they exhibit catalytic activity for the dehydrogenative C-methylation of piperidine with methanol, to yield 3-methylpyridine. At 400°C, the selectivity is as high as 74%. This catalytic behavior is different from that of the molecular clusters [(M6Cl12)Cl2(H2O)4]?4H2O (M= Nb, Ta) and (H3O)2[(M6Cl8)Cl6]?6H2O (M= Mo, W), which exhibit Bronsted acidity after thermal activation; piperidine is N-methylated to yield N-methylpiperidine selectively. Elemental analysis and thermogravimetric analysis demonstrate that the solid-state clusters partially eliminate halogen ligands during the activation. Infrared analysis of adsorbed pyridine on the activated clusters shows the presence of a Lewis acid site. This coordinatively unsaturated site of the molybdenum is catalytically active for dehydrogenative C-methylation. The formation of an η3-1-azaallyl species on the molybdenum facilitates the methylation at the 3-position of piperidine, followed by dehydrogenation to yield 3-methylpyridine.
- Kamiguchi, Satoshi,Kajio, Ryu,Yamada, Hitomi,Yuge, Hidetaka,Okumura, Kazu,Iida, Hajime,Nagashima, Sayoko,Chihara, Teiji
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p. 1116 - 1122
(2015/09/01)
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- Boron-Catalyzed N-Alkylation of Amines using Carboxylic Acids
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A boron-based catalyst was found to catalyze the straightforward alkylation of amines with readily available carboxylic acids in the presence of silane as the reducing agent. Various types of primary and secondary amines can be smoothly alkylated with good selectivity and good functional-group compatibility. This metal-free amine alkylation was successfully applied to the synthesis of three commercial medicinal compounds, Butenafine, Cinacalcet. and Piribedil, in a one-pot manner without using any metal catalysts.
- Fu, Ming-Chen,Shang, Rui,Cheng, Wan-Min,Fu, Yao
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supporting information
p. 9042 - 9046
(2015/08/03)
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- Sustainable heterogeneous platinum catalyst for direct methylation of secondary amines by carbon dioxide and hydrogen
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Pt and MoOx co-loaded TiO2 is found to be highly effective for direct methylation of aliphatic and aromatic secondary amines by CO2 and H2 under solvent-free conditions. This is the first additive-free and reusable heterogeneous catalytic system with acceptable turnover number. Over and over: A heterogeneous Pt catalyst for direct methylation of aromatic amines by CO2 and H2 with high reusability and an order of magnitude higher turnover number than previous catalysts has been demonstrated (see scheme).
- Kon, Kenichi,Siddiki, S. M. A. Hakim,Onodera, Wataru,Shimizu, Ken-Ichi
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p. 6264 - 6267
(2014/06/09)
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- N-Methylation of amine and nitro compounds with CO2/H2 catalyzed by Pd/CuZrOx under mild reaction conditions
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An active Pd/ZrCuOx catalyst was prepared for the reductive amination of CO2. The N-methylation of amines and nitro compounds with CO2/H2 can be realized with up to 97% yield under relatively mild reaction condi
- Cui, Xinjiang,Zhang, Yan,Deng, Youquan,Shi, Feng
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supporting information
p. 13521 - 13524
(2015/01/09)
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- Carbon Dioxide Reduction to Methylamines under Metal-Free Conditions
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The first metal-free catalysts are reported for the methylation of amines with carbon dioxide. Proazaphosphatrane superbases prove to be highly active catalysts in the reductive functionalization of CO2, in the presence of hydroboranes. The new methodology enables the methylation of N-H bonds in a wide variety of amines, including secondary amines, with increased chemoselectivity. Organocatalysis: Proazaphosphatrane superbases prove to be highly active catalysts in the reductive functionalization of CO2, in the presence of hydroboranes. The new method makes possible the methylation of N-H bonds in a wide variety of amines, including secondary amines (see picture), with increased chemoselectivity.
- Blondiaux, Enguerrand,Pouessel, Jacky,Cantat, Thibault
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p. 12186 - 12190
(2016/02/23)
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- Amino-alcohol cyclization: Selective synthesis of lactams and cyclic amines from amino-alcohols
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By employing an amination catalyst, previously used in the direct synthesis of amines from alcohol with ammonia, n-amino-alcohols could be selectively cyclized to either the amide or the amine. By the addition of water, the amine could be produced as the major product whereas adding a sacrificial ketone as a hydrogen acceptor resulted in the amide as the major product. Without an additive a mixture of both the amine and the amide was observed. N-substituted amino-alcohols solely gave cyclic amines under these conditions. From 2-(n-alkanol) anilines the cyclic amines were produced, where the n-propanol derivative selectively formed quinoline as the major product.
- Pingen, Dennis,Vogt, Dieter
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- Stabilization of the pesticide Fenitrothion toward O and N nucleophiles in the presence of cyclodextrins
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The reaction of Fenitrothion with O and N nucleophiles (H2O2, NH2OH, n-butylamine and piperidine) was studied at 25°C in water containing 2% 1,4-dioxane in the presence of native cyclodextrins (α-, β-, and γ-CD). For all the nucleophiles, the presence of CD produces reaction inhibition with saturation kinetics. The greatest effect in all cases is observed with β-CD, and the greatest inhibition was observed for the reaction of Fenitrothion with H2O2 (81%), which is the most efficient nucleophile in promoting Fenitrothion degradation in homogeneous media. In the absence of CD, competition between the SN2(P) and the SN2(C) pathways was observed with piperidine as was reported before for the reaction with NH2OH and n-butylamine. The presence of β-CD does not modify product distribution in the case of the reaction with NH2OH and n-butylamine, whereas there is an increase in SN2(C) pathway when the nucleophile is piperidine.
- Rougier, Natalia M.,Vico, Raquel V.,De Rossi, Rita H.,Bujn, Elba I.
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supporting information
p. 935 - 943
(2015/02/19)
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- Methylation of amines, nitrobenzenes and aromatic nitriles with carbon dioxide and molecular hydrogen
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CO2/H2 was successfully employed in alkylation reactions by performing CO2 reduction and amine N-methylation in one-pot. In the presence of a simple CuAlOx catalyst, N-methyl or N,N-dimethyl amines with different structures can be selectively synthesized with up to 96% yields by applying amine, nitrobenzene and nitrile as starting materials.
- Cui, Xinjiang,Dai, Xingchao,Zhang, Yan,Deng, Youquan,Shi, Feng
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p. 649 - 655
(2014/01/17)
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- Catalytic hydrogenation of amides to amines under mild conditions
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Under (not so much) pressure: A general method for the hydrogenation of tertiary and secondary amides to amines with excellent selectivity using a bimetallic Pd-Re catalyst has been developed. The reaction proceeds under low pressure and comparatively low temperature. This method provides organic chemists with a simple and reliable tool for the synthesis of amines. Copyright
- Stein, Mario,Breit, Bernhard
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supporting information
p. 2231 - 2234
(2013/03/28)
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- Cesium carbonate-catalyzed reduction of amides with hydrosilanes
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Cesium carbonate has been found to be an effective catalyst for the reduction of tertiary carboxamides with the simple, commercially available PhSiH3 under solvent-free conditions. The catalytic system can effectively reduce a range of amides under relatively mild conditions (from room temperature to 80 C) to yield the corresponding amines in good to excellent yields (71-100%) and thus has the potential for practical applications.
- Xie, Weilong,Zhao, Mengdi,Cui, Chunming
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p. 7440 - 7444
(2014/04/03)
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- A practical regioselective synthesis of alkylthio- or arylthioindoles without the use of smelly compounds such as thiols
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A convenient method for the synthesis of 3-methylthioindoles has been established which does not use smelly compounds such as thiol derivatives. The method, which introduces an alkyl- or arylthio-group into the C3-position of the indole skeleton, was extended to the direct introduction of a methylthio or bromo group at the C2-position using 3-methylthioindoles. No dimerization occurred, and the reaction mechanism was confirmed. The products have the partial structure of potent anti-methicillin-resistant Staphylococcus aureus (anti-MRSA) bromomethylthioindoles (MC 5-8) isolated from marine algae. Furthermore, this reaction could be applied to the synthesis of 3,3-diindolyl thioether which is a core structure of Echinosulfone A.
- Hamashima, Toshihiko,Mori, Yoshiaki,Sawada, Kazunori,Kasahara, Yuko,Murayama, Daisuke,Kamei, Yuto,Okuno, Hiroaki,Yokoyama, Yuusaku,Suzuki, Hideharu
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p. 292 - 303
(2013/05/08)
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- Amination of aliphatic alcohols catalyzed by CuO-NiO/γ-Al 2O3
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The amination of aliphatic alcohols in the gas-solid phase was investigated in a fixed-bed reactor in the presence of CuO-NiO/γ-Al2O 3 as the catalyst. This catalytic system was successfully applied for both the N-methylation of aliphatic amines and N-alkylation of piperidine with primary or secondary alcohols. N-Alkylation of piperidine with low-carbon alcohols resulted in high conversions and selectivities, and the conversion of piperidine and the selectivities toward the desired products declined gradually with the increase of the carbon number of aliphatic alcohols. The influence of varied conditions on the N-cyclohexylation of piperidine was also evaluated, including liquid hourly space velocity (LHSV), temperature and the catalyst; especially the catalyst had the greatest impact. Finally, the test of the catalyst's stability was performed.
- Huang, Jia-Min,Qian, Chao,Feng, Lie,Chen, Yun-Bin,Chen, Xin-Zhi
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p. 1187 - 1190
(2013/08/23)
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- CO2 as a C1-building block for the catalytic methylation of amines
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A novel catalytic reaction has been designed to utilize, for the first time, CO2 as a C1 feedstock in the synthesis of N-methylamines. Simple zinc catalysts, based on commercially available zinc salts and ligands, prove highly efficient in promoting both a 6 electron reduction of carbon dioxide and the formation of a C-N bond, using hydrosilanes and amines.
- Jacquet, Olivier,Frogneux, Xavier,Das Neves Gomes, Christophe,Cantat, Thibault
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p. 2127 - 2131
(2013/05/21)
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