- Method for preparing amine compound by reducing amide compound
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The invention relates to a method for preparing an amine compound by reducing an amide compound, which comprises the following steps: in a protective atmosphere, mixing the amide compound or cyclic amide, a zirconium metal catalyst and pinacol borane, carrying out amide reduction reaction at room temperature, and carrying out aftertreatment by using an ether solution of hydrogen chloride after 12-48 hours to obtain an amine hydrochloride compound. The method is simple to operate, low in cost, good in functional group tolerance and wide in substrate range.
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Paragraph 0115-0117
(2021/02/10)
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- Zirconium-hydride-catalyzed site-selective hydroboration of amides for the synthesis of amines: Mechanism, scope, and application
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Developing mild and efficient catalytic methods for the selective synthesis of amines is a longstanding research objective. In this respect, catalytic deoxygenative amide reduction has proven to be promising but challenging, as this approach necessitates selective C–O bond cleavage. Herein, we report the selective hydroboration of primary, secondary, and tertiary amides at room temperature catalyzed by an earth-abundant-metal catalyst, Zr-H, for accessing diverse amines. Various readily reducible functional groups, such as esters, alkynes, and alkenes, were well tolerated. Furthermore, the methodology was extended to the synthesis of bio- and drug-derived amines. Detailed mechanistic studies revealed a reaction pathway entailing aldehyde and amido complex formation via an unusual C–N bond cleavage-reformation process, followed by C–O bond cleavage.
- Han, Bo,Jiao, Haijun,Wu, Lipeng,Zhang, Jiong
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p. 2059 - 2067
(2021/09/02)
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- Boosting Mass Exchange between Pd/NC and MoC/NC Dual Junctions via Electron Exchange for Cascade CO2 Fixation
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Merging existing catalysts together as a cascade catalyst may achieve one-pot synthesis of complex but functional molecules by simplifying multistep reactions, which is the blueprint of sustainable chemistry with low pollutant emission and consumption of energy and materials only when the smooth mass exchange between different catalysts is ensured. Effective strategies to facilitate the mass exchange between different active centers, which may dominate the final activity of various cascade catalysts, have not been reached until now, even though charged interfaces due to work function driven electron exchange have been widely observed. Here, we successfully constructed mass (reactants and intermediates) exchange paths between Pd/N-doped carbon and MoC/N-doped carbon induced by interfacial electron exchange to trigger the mild and cascade methylation of amines using CO2and H2. Theoretical and experimental results have demonstrated that the mass exchange between electron-rich MoC and electron-deficient Pd could prominently improve the production of N,N-dimethyl tertiary amine, which results in a remarkably high turnover frequency value under mild conditions, outperforming the state-of-the-art catalysts in the literature by a factor of 5.9.
- Chen, Jie-Sheng,Li, Qi-Yuan,Li, Xin-Hao,Lin, Xiu,Xia, Si-Yuan,Xu, Dong,Zhai, Guang-Yao,Zhang, Shi-Nan
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supporting information
(2022/03/15)
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- Deoxygenative hydroboration of primary, secondary, and tertiary amides: Catalyst-free synthesis of various substituted amines
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Transformation of relatively less reactive functional groups under catalyst-free conditions is an interesting aspect and requires a typical protocol. Herein, we report the synthesis of various primary, secondary, and tertiary amines through hydroboration of amides using pinacolborane under catalyst-free and solvent-free conditions. The deoxygenative hydroboration of primary and secondary amides proceeded with excellent conversions. The comparatively less reactive tertiary amides were also converted to the corresponding N,N-diamines in moderate yields under catalyst-free conditions, although alcohols were obtained as a minor product.
- An, Duk Keun,Jaladi, Ashok Kumar,Kim, Hyun Tae,Yi, Jaeeun
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- Carbon dioxide transformation in imidazolium salts: Hydroaminomethylation catalyzed by Ru-complexes
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The catalytic species generated by dissolving Ru3(CO)12 in the ionic liquids 1-n-butyl-3-methyl-imidazolium chloride or 1-n-butyl-2,3-dimethyl-imidazolium chloride are efficient multifunctional catalysts for: (a) reverse water-gas shift, (b) hydroformylation of alkenes, and (c) reductive amination of aldehydes. Thus the reaction of alkenes with primary or secondary amines (alkene/amine, 1:1) under CO2/H2 (1:1) affords the hydroamino-methylations products in high alkene conversions (up to 99%) and selectivities (up to 96%). The reaction proceeds under relatively mild reaction conditions (120 °C, 60 bar = 6 MPa) and affords selectively secondary and tertiary amines. The presence of amine strongly reduces the alkene hydrogenation competitive pathway usually observed in the hydroformylation of terminal alkenes by Ru complexes. The catalytic system is also highly active for the reductive amination of aldehydes and ketones yielding amines in high yields (> 90%).
- Ali, Meher,Gual, Aitor,Ebeling, Gunter,Dupont, Jairton
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p. 2129 - 2134
(2017/07/25)
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- Methylformate as replacement of syngas in one-pot catalytic synthesis of amines from olefins
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A new general approach for the one-pot hydroaminomethylation of olefins using methylformate as formylating agent instead of synthesis gas (syngas) has been proposed. Herein we report that a Ru-Rh catalytic system demonstrates high activity in a tandem conversion of a series of n-alkenes into amines using methylformate with yields 58-92% (6 h). The selectivity for the normal amine reached 96% with catalysis by the Ru carbonyl complex Ru3(CO) 12, with an overall yield of 55% with respect to amine in this instance. The addition of the Rh complex to Ru catalytic system, sharply increased the hydroaminomethylation rate of both the terminal and internal alkenes and increased the yield of amines to 82-93% (6-12 h). The Royal Society of Chemistry.
- Karakhanov, Eduard,Maksimov, Anton,Kardasheva, Yulia,Runova, Elena,Zakharov, Roman,Terenina, Maria,Kenneally, Corey,Arredondo, Victor
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p. 540 - 547
(2014/02/14)
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- New catalyst systems for iron-catalyzed hydrosilane reduction of carboxamides
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A heptanuclear iron carbonyl cluster, [Fe3(CO) 11(μ-H)]2Fe(DMF)4 (4), is found to be a highly efficient catalyst for the reduction of various carboxamides by 1,2-bis(dimethylsilyl)benzene (BDSB), which makes possible reducing the amount of the catalyst, shortening the reaction time, and lowering the reaction temperatures.
- Tsutsumi, Hironori,Sunada, Yusuke,Nagashima, Hideo
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supporting information; experimental part
p. 6581 - 6583
(2011/07/08)
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- Selective hydrogenation of amides using ruthenium/ molybdenum catalysts
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Recyclable, heterogeneous bimetallic ruthenium/molybdenum catalysts, formed in situ from triruthenium dodecacarbonyl [Ru3(CO)12] and molybdenum hexacarbonyl [Mo(CO)6], are effective for the selective liquid phase hydrogenation of cyclohexylcarboxamide (CyCONH2) to cyclohexanemethylamine (CyCH2NH2), with no secondary or tertiary amine by-product formation. Variation of Mo:Ru composition reveals both synergistic and poisoning effects, with the optimum combination of conversion and selectivity at ca. 0.5, and total inhibition of catalysis evident at ≥1. Good amide conversions are noted within the reaction condition regimes 20100 bar hydrogen and 145-160°C. The order of reactivity of these catalysts towards reduction of different amide functional groups is primary > tertiary ? secondary. In situ HP-FT-IR spectroscopy confirms that catalyst genesis occurs during an induction period associated with decomposition of the organometallic precursors. Ex situ characterisation, using XRD, XPS and EDX-STEM, for active Mo:Ru compositions, has provided evidence for intimately mixed ca. 2.5-4 nm particles that contain metallic ruthenium, and molybdenum (in several oxidation states, including zero).
- Beamson, Graham,Papworth, Adam J.,Philipps, Charles,Smith, Andrew M.,Whyman, Robin
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experimental part
p. 869 - 883
(2010/07/05)
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- Hydrosilane reduction of tertiary carboxamides by iron carbonyl catalysts
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Fox in the carboxamide: Reduction of tertiary carboxamides to their corresponding amines is catalyzed by [Fe(CO)5] or [Fe 3(CO)12], using 1,1,3,3tetramethyldlsiloxane (TMDS) as the reducing agent. The reaction proceeds under either thermal or photochemical conditions. Unlike the hydrosilane reduction of amides using platinum or ruthenlum catalysts, TMDS preferentially reduces a nitro group, even in the presence of competing amides.
- Sunada, Yusuke,Kawakami, Hiroko,Imaoka, Tsuyoshi,Motoyama, Yukihiro,Nagashima, Hideo
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supporting information; experimental part
p. 9511 - 9514
(2010/03/24)
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- Practical access to amines by platinum-catalyzed reduction of carboxamides with hydrosilanes: Synergy of dual Si-H groups leads to high efficiency and selectivity
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The synergetic effect of two Si-H groups leads to efficient reduction of carboxamides to amines by platinum catalysts under mild conditions. The rate of the reaction is dependent on the distance of two Si-H groups; 1,1,3,3-tetramethyldisiloxane (TMDS) and 1,2-bis(dimethylsilyl)benzene are found to be an effective reducing reagent. The reduction of amides having other reducible functional groups such as NO2, CO2R, CN, CdC, Cl, and Br moieties proceeds with these groups remaining intact, providing a reliable method for the access to functionalized amine derivatives. The platinum-catalyzed reduction of amides with polymethylhydrosiloxane (PMHS) also proceeds under mild conditions. The reaction is accompanied by automatic removal of both platinum and silicon wastes as insoluble silicone resin, and the product is obtained by simple extraction. A mechanism involving double oxidative addition of TMDS to a platinum center is discussed.
- Hanada, Shiori,Tsutsumi, Emi,Motoyama, Yukihiro,Nagashima, Hideo
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supporting information; scheme or table
p. 15032 - 15040
(2010/01/29)
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- Ruthenium-catalyzed /V-alkylation of amines and sulfonamides using borrowing hydrogen methodology
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The alkylation of amines by alcohols has been achieved using 0.5 mol percent [Ru(p-cymene)CI2]2 with the bidentate phosphines dppf or DPEphos as the catalyst. Primary amines have been converted into secondary amines, and secondary amines into tertiary amines, including the syntheses of Piribedil, Tripelennamine, and Chlorpheniramine. A/-Heterocyclization reactions of primary amines are reported, as well as alkylation reactions of primary sulfonamides. Secondary alcohols requiremore forcing conditions than primary alcohols but are still effective a lkylating agents in the presence of this catalyst.
- Hamid, M. Haniti S. A.,Allen, C. Liana,Lamb, Gareth W.,Maxwell, Aoife C.,Maytum, Hannah C.,et al.
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supporting information; experimental part
p. 1766 - 1774
(2009/07/25)
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- Aminomethylation of organic halides promoted by zinc in protic medium
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Organic halides undergo smooth aminomethylation by secondary amines and aqueous formaldehyde promoted by metallic zinc under copper(I) catalysis. Good to excellent yields are obtained with primary, secondary, and tertiary iodides, allylic, propargylic, and benzylic bromides and with α-bromoesters. In most cases, DMSO is the best solvent, but dioxane is preferable for some more reactive halides. Additional experiments with radical quenchers and promoters and the use of 'radical clocks' indicate a stepwise reaction mechanism initiated by the attack of an alkyl radical to iminium ion.
- Estevam, Idália H. S.,Da Silva, Margarete F.,Bieber, Lothar W.
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p. 7601 - 7604
(2007/10/03)
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- Compounds
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Polystyrene polymers of structure : in which, R1 and R2 are the same or different and are each C1 4 alkyl; R3 is (CH2)nR4 in which R4 is C3 6 cycloalkyl or a bicyclic carbocyclic ring of up to 10 carbon atoms and n is 1 to 12, or R3 is (CH2)nCH = R5R6 in which n is 1 to 12 and R5 and R6 together form a C3 6 cycloalkyl ring or a bicyclic carbocyclic ring of up to 10 carbon atoms; R7 is hydrogen or a group CH2N R1R2R3X ; X is a counter ion; a, b and c are numbers which indicate the relative molar percentages of the units present in said polymer, (b) being from about 1 to about 10 molar percent, and (c) being from about 30 to about 98 molar percent; m is a number indicating the degree of polymerisation of said polymer, processes for their preparation, compositions containing them and their use in therapy as bile acid sequestering agents.
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- Aminoborohydrides as Reducing Agents. 1. Sodium (Dimethylamino)- and (tert-Butylamino)borohydrides as Selective Reducing Agents
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Replacement of a hydride in borohydride by an electron-donating alkylamino group greatly enhances the reducing ability of the resulting reagents.Thus, sodium (dimethylamino)- and (tert-butylamino)borohydrides (1, NaDMAB, and 2, NaTBAB, respectively) not only reduce aldehydes and ketones to alcohols but also are effective for the conversion of esters to alcohols and primary amides to amines in good to excellent yields.Tertiary amides are reduced to alcohols (i.e., N,N-dimethylamides) or amines (i.e.N,N-diisopropylamides) depending on the steric bulk of the alkyl substituents on nitrogen.However, secondary amides are not reduced by the reagents allowing selective conversion of primary and tertiary amides in the presence of secondary amides.Nitriles are attacked by the reagents but do not afford synthetically useful amounts of amine products.Aryl halides are slowly converted to arenes, but alkyl halides and epoxides undergo unusual reactions with the amino portion of the reagents.
- Hutchins, Robert O.,Learn, Keith,El-Telbany, Farag,Stercho, Yuriy P.
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p. 2438 - 2443
(2007/10/02)
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- Selective Reductions. 29. A Simple Technique To Achieve an Enhanced Rate of Reduction of Representative Organic Compounds by Borane-Dimethyl Sulfide
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A dramatic increase in the rate of reduction of esters by borane-dimethyl sulfide (BMS) is observed when dimethyl sulfide is removed from the reaction mixture.On the basis of this observation, a new, improved procedure has been developed for the reduction by BMS of representative organic functional groups, such as esters, nitriles, and amides.The procedure involves addition of BMS to the substrate in refluxing tetrahydrofuran, allowing the liberated dimethyl sulfide to distill off during the reaction.Stoichiometric studies established the minimum amount of BMS required for the complete reduction of these functional groups.Thus, esters require 2 equiv of hydride (HBC=O to >CH2.Employing this stoichiometry, the reduction of aliphatic esters is quite rapid, complete in 0.5 h, while the reduction of aromatic esters is slower, requiring 4-16 h.The corresponding alcohols are produced in excellent yields.On the other hand, nitriles require 3 equiv of hydride (one borane unit/nitrile) and are reduced rapidly in 0.25 h to the corresponding borazine complex, readily hydrolyzed to the corresponding amines.On the other hand, amides require different equivalents of hydride, depending on the particular type of amide undergoing reduction.Thus, tertiary amides require 5 equiv of hydride and form the amine-borane adducts in 0.25 h.Secondary amides liberate hydrogen prior to forming the amine-borane complex, utilizing 6 equiv of hydride in 0.25-1.0 h.However, primary amides require only 4 equiv of hydride, 2 for hydrogen liberation and 2 for reduction, producing in 1.0-2.0 h the amine dibora derivatives, which are sufficiently weakly basic as not to complex with BMS.The ease of reduction of amides follows the order tertiarysecondary>primary.A simple procedure has been described for the reduction of tertiary and secondary amides using decreased amounts of BMS in the presence of boron trifluoride etherate.Unlike lithium aluminum hydride, super hydride, etc., the tendency for C-N bond cleavage to produce the alcohol is completely absent in these reductions of BMS.The reagent permits the presence of many common substituents, such as nitro, chloro, methoxy, etc.The reaction is not significantly susceptible to electronic and steric effects.Simple procedures have been developed for isolating the products.This study establishes a convenient synthetic route for the selective reduction of various organic functional groups with BMS where this transformation is desired in synthetic operations.
- Brown, Herbert C.,Moon Choi, Yong,Narasimhan, S.
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p. 3153 - 3163
(2007/10/02)
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- Scope and Pathway of Catalytic Aminomethylation of Olefins
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We describe a general and high-yield one-step process for synthesis of tertiary and secondary amines from olefins, carbon monoxide, water, and a nitrogen source in the presence of transition-metal compounds as catalysts.We find this chemistry, initially d
- Jachimowicz, Felek,Raksis, Joseph W.
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p. 445 - 447
(2007/10/02)
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