- Photoinduced electron-transfer reaction of α-bromomethyl-substituted benzocyclic β-keto esters with amines: Selective reaction pathways depending on the nature of the amine radical cations
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Photoinduced electron-transfer reaction of α-bromomethyl-substituted benzocyclic β-keto esters with tertiary amines was investigated. Debrominated β-keto esters and ring-expanded γ-keto esters were obtained as major products. On the basis of mechanistic experiments it was concluded that these products are formed via a reaction sequence of selective carbon-bromine bond cleavage and subsequent competitive hydrogen abstraction and Dowd-Beckwith ring-expansion of the resulting primary alkyl radicals. The characteristic product distribution observed for the type of amine used is rationalized on the basis of selective reaction pathways of generated radical intermediates that depend on the nature of the amine radical cations.
- Hasegawa, Eietsu,Tosaka, Emi,Yoneoka, Akira,Tamura, Yukinobu,Takizawa, Shin-Ya,Tomura, Masaaki,Yamashita, Yoshiro
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Read Online
- A potassium magnesiate complex: Synthesis, structure and catalytic intermolecular hydroamination of styrenes
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A new heterobimetallic potassium magnesiate complex KMg[N(SiMe3)2]2Bn (Bn = PhCH2-) was synthesized by simply mixing magnesium amide and potassium benzyl in toluene. The TMEDA-ligated potassium magnesiate comple
- Guan, Bing-Tao,Liu, Yu-Feng,Zhai, Dan-Dan,Zhang, Xiang-Yu
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supporting information
(2022/01/19)
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- Structure-Activity Relationship Studies of Pyrimidine-4-Carboxamides as Inhibitors of N-Acylphosphatidylethanolamine Phospholipase D
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N-Acylphosphatidylethanolamine phospholipase D (NAPE-PLD) is regarded as the main enzyme responsible for the biosynthesis of N-acylethanolamines (NAEs), a family of bioactive lipid mediators. Previously, we reported N-(cyclopropylmethyl)-6-((S)-3-hydroxypyrrolidin-1-yl)-2-((S)-3-phenylpiperidin-1-yl)pyrimidine-4-carboxamide (1, LEI-401) as the first potent and selective NAPE-PLD inhibitor that decreased NAEs in the brains of freely moving mice and modulated emotional behavior [ Mock et al. Nat Chem. Biol., 2020, 16, 667-675 ]. Here, we describe the structure-activity relationship (SAR) of a library of pyrimidine-4-carboxamides as inhibitors of NAPE-PLD that led to the identification of LEI-401. A high-throughput screening hit was modified at three different substituents to optimize its potency and lipophilicity. Conformational restriction of an N-methylphenethylamine group by replacement with an (S)-3-phenylpiperidine increased the inhibitory potency 3-fold. Exchange of a morpholine substituent for an (S)-3-hydroxypyrrolidine reduced the lipophilicity and further increased activity by 10-fold, affording LEI-401 as a nanomolar potent inhibitor with drug-like properties. LEI-401 is a suitable pharmacological tool compound to investigate NAPE-PLD function in vitro and in vivo.
- Mock, Elliot D.,Kotsogianni, Ioli,Driever, Wouter P. F.,Fonseca, Carmen S.,Vooijs, Jelle M.,Den Dulk, Hans,Van Boeckel, Constant A. A.,Van Der Stelt, Mario
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p. 481 - 515
(2021/02/05)
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- Method for synthesizing dibenzylamine compound by selective hydrogenation of photocatalytic benzonitrile compound
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The invention belongs to the technical field of selective catalytic hydrogenation, and particularly relates to a method for synthesizing a dibenzylamine compound through selective hydrogenation of a photocatalytic benzonitrile compound, wherein the photocatalyst is prepared from silicon carbide with high specific surface area (specific surface area 20 - 100m). 2 Metal Platinum as a carrier load mass fraction 0.1-20%, the metal nanoparticles being less than 200 nanometers ?. g. After mixing the benzonitrile compound and the solvent at 0.01 - 0.6 mass ratio, the catalyst was added, and the hydrogen pressure was maintained between 0.1 mpa - 2 mpa under hydrogen atmosphere and the reaction was stirred while maintaining the temperature of the reaction system was 10 - 100 °C and the strength was 0.01 - 5W/cm. 2 Under the light intensity of the reaction 0.5 - 12h, the target product can be obtained. The method has the most remarkable characteristics of being capable of effectively utilizing light to promote reaction and high in reaction rate.
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Paragraph 0044-0047
(2021/09/29)
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- Rhodium-Catalyzed Anti-Markovnikov Hydroamination of Aliphatic and Aromatic Terminal Alkynes with Aliphatic Primary Amines
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Anti-Markovnikov hydroamination of both aliphatic and aromatic terminal alkynes with primary amines was achieved using an 8-quinolinolato rhodium catalyst to form aldimines and enamines in high yields. This catalytic system realized high functional group tolerance including hydroxy, bromo, cyano, and thioester groups.
- Kakiuchi, Fumitoshi,Kochi, Takuya,Morimoto, Yoshihiko
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p. 13143 - 13152
(2021/09/28)
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- Selective Synthesis of Symmetrical Secondary Amines from Nitriles with a Pt?CuFe/Fe3O4 Catalyst and Ammonia Borane as Hydrogen Donor
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Hydrogenation of nitriles is an efficient and environmentally friendly route to synthesize symmetrical secondary amines, but it usually produces a mixture of amines, imines, and hydrogenolysis by-products. Herein we report a magnetic quaternary-component Pt?CuFe/Fe3O4 nanocatalyst system for the selective synthesis of symmetrical secondary amines with ammonia borane as hydrogen donor. The catalyst with a low Pt loading (0.456 wt%) is the source of the activity, and the d-band electron transfer from Cu to Fe enhances the selectivity. This synergistic effect results in the transformation of benzonitrile to dibenzylamine with excellent conversion (up to 99 %) and nearly quantitative selectivity (up to 96 %) under mild reaction conditions, nevertheless, the reaction TOF is as high as up to 1409.9 h?1. A variety of nitriles are suitable for the synthesis of symmetrical secondary amines. More importantly, unwanted hydrogenolysis byproducts, especially toluene, is not detected at all. In addition, the catalyst is magnetically recoverable, and it can be reused up to five times.
- Ai, Yongjian,Guo, Rongxiu,He, GuangQi,Hu, Ze-nan,Liang, Qionglin,Liu, Lei,Niu, Dun,Sun, Hong-bin,Tian, Haimeng,Zhang, Xinyue
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p. 1783 - 1788
(2020/09/02)
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- Catalytic Hydrogenation of Thioesters, Thiocarbamates, and Thioamides
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Direct hydrogenation of thioesters with H2 provides a facile and waste-free method to access alcohols and thiols. However, no report of this reaction is documented, possibly because of the incompatibility of the generated thiol with typical hydrogenation catalysts. Here, we report an efficient and selective hydrogenation of thioesters. The reaction is catalyzed by an acridine-based ruthenium complex without additives. Various thioesters were fully hydrogenated to the corresponding alcohols and thiols with excellent tolerance for amide, ester, and carboxylic acid groups. Thiocarbamates and thioamides also undergo hydrogenation under similar conditions, substantially extending the application of hydrogenation of organosulfur compounds.
- Luo, Jie,Rauch, Michael,Avram, Liat,Ben-David, Yehoshoa,Milstein, David
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supporting information
p. 21628 - 21633
(2021/01/11)
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- Cine-Silylative Ring-Opening of α-Methyl Azacycles Enabled by the Silylium-Induced C-N Bond Cleavage
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Described herein is the development of a borane-catalyzed cine-silylative ring-opening of α-methyl azacycles. This transformation involves four-step cascade processes: (i) exo-dehydrogenation of alicyclic amine, (ii) hydrosilylation of the resultant enamine, (iii) silylium-induced cis-β-amino elimination to open the ring skeleton, and (iv) hydrosilylation of the terminal olefin. The present borane catalysis also works efficiently for the C-N bond cleavage of acyclic tertiary amines. On the basis of experimental and computational studies, the silicon atom was elucidated to play a pivotal role in the β-amino elimination step.
- Zhang, Jianbo,Chang, Sukbok
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supporting information
p. 12585 - 12590
(2020/08/21)
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- Application of nano-carbon supported monatomic palladium-based catalyst in catalytic hydrogenation of nitrile compound to prepare secondary amine
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The invention discloses application of a nano-carbon supported monatomic palladium-based catalyst in catalytic hydrogenation of a nitrile compound to prepare a secondary amine and belongs to the technical field of catalysts with application of catalytic hydrogenation of liquid-phase nitrile compounds. By adopting the monatomically dispersed palladium-based catalyst, a corresponding secondary aminecompound is generated with high selectivity under a mild condition, and the catalysis reaction conditions are that the reaction temperature is 45-90 DEG C and ammonia borane is adopted as a hydrogensource. In the catalyst disclosed by the invention, metals exist in a monatomic dispersion state, so that the utilization efficiency of the metals can be effectively improved, and the activity and theselectivity of the nitrile compound can be remarkably improved. In addition, the monatomically dispersed catalyst is convenient to prepare and low in cost, and has very good application prospects incatalytic hydrogenation of the nitrile compound to prepare the secondary amine.
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Paragraph 0042; 0043; 0050; 0051
(2020/03/06)
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- Method for preparing secondary amines through hydrogen transferring selective nitrile reduction
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The invention discloses a method for preparing secondary amines through hydrogen transferring selective nitrile reduction. According to the method, nitrile compounds (including aryl nitrile derivatives, chain and cyclic aliphatic nitrile and the like) are taken as raw materials, oxazaborolidine is taken as a hydrogen transferring agent, low-price copper and ferric metal salt are taken as additivesto catalyze the nitrile compounds to perform hydrogen transferring reaction, and therefore a corresponding secondary amine product is prepared, wherein the oxazaborolidine is prepared by the reactionof amino alcohol and a tetrahydrofuran complex of borane. The method has the advantages that the reaction condition is simple and mild, a low-price copper salt is taken as a catalyst, alkali is takenas an additive, and reduction reaction can be conducted combining with the nitrile and the hydrogen transferring agent, the reduction product is the secondary amine only, the selectivity is good, theyield is high, the hydrogen transferring agent, the additive and the catalyst are low in price and easy to obtain, the method is green and environmentally friendly, the operation is safe, the reproducibility is high, and effective schemes are provided for subsequent industrial production.
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Paragraph 0057; 0058; 0059; 0060
(2019/05/04)
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- Iron-Catalyzed Intramolecular C-H Amination of α-Azidyl Amides
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Iron-catalyzed intramolecular C-H amination of aliphatic azides has recently emerged as a powerful tool for the preparation of nitrogen heterocycles. This paper reports that α-azidyl amides can be converted in high efficacy to imidazolinone compounds via intramolecular C(sp3)-H amination by the action of a simple catalytic system composed of FeCl2 and a β-diketiminate ligand. The reactions provide a simple and atom-economical approach toward polysubstituted imidazolinones.
- Zhao, Xiaopeng,Liang, Siyu,Fan, Xing,Yang, Tonghao,Yu, Wei
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supporting information
p. 1559 - 1563
(2019/03/20)
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- Pd/TiO2-Photocatalyzed Self-Condensation of Primary Amines to Afford Secondary Amines at Ambient Temperature
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Symmetric secondary amines were synthesized by the self-condensation of primary amines over a palladium-loaded titanium dioxide (Pd/TiO2) photocatalyst. The reactions afforded a series of secondary amines in moderate to excellent isolated yields at ambient temperature (30 °C, in cyclopentyl methyl ether). Applicability for one-pot pharmaceutical synthesis was demonstrated by a photocatalytic reaction sequence of self-condensation of an amine followed by N-alkylation of the resulting secondary amine with an alcohol.
- Wang, Lyu-Ming,Kobayashi, Kensuke,Arisawa, Mitsuhiro,Saito, Susumu,Naka, Hiroshi
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supporting information
p. 341 - 344
(2018/12/11)
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- INHIBITORS OF N-ACYLPHOSPHATIDYLETHANOLAMINE PHOSPHOLIPASE D (NAPE-PLD)
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The invention relates to a compound of the formula (I) as novel inhibitor of N-acylphosphatidylethanolamine phospholipase D (NAPE-PLD), and to use thereof for the prophylaxis or treatment of diseases associated with NAPE-PLD. wherein in a ring A, X1 is N, or CR4; X2 is N or CR5; X3 is N or CH; with the proviso that at least one of X1 and X3 is N.
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- Chemoselective hydrogenation of nitriles to primary amines catalyzed by water-soluble transition metal catalysts
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The water-soluble rhodium complex generated in situ from [Rh (COD)Cl]2 in aqueous ammonia has been revealed as a highly efficient catalyst for the hydrogenation of aromatic nitriles, to primary amines with excellent yields. The catalyst is also highly selective towards primary amines in the case of sterically hindered aliphatic nitriles. The catalytic system can also be recycled and re-used with no significant loss of activity.
- Nait Ajjou, Abdelaziz,Robichaud, André
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- Diphenethylamine Derivatives Which Are Inter Alia Useful As Analgesics And Method For Their Production
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Diphenethylamine derivatives for use as highly active analgesics, diuretics, anxiolytics, for the treatment of neurode-generative, psychiatric and neuropsychiatric disorders, and also as anti-itch, anti-addiction, anti-inflammatory, anti-obesity, anti-epi
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- Cobalt complex, preparation method thereof, and application thereof in selective catalysis of transfer hydrogenation reaction of cyano group
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The invention discloses a cobalt complex, a preparation method thereof, and an application thereof in the selective catalysis of a transfer hydrogenation reaction of a cyano group. The structural formula of the cobalt complex is represented by formula I. The cobalt complex is prepared through a reaction of a cobalt salt and an NNP ligand or a PNP ligand under the protection of an inert atmosphere;and the chemical formula of the cobalt salt is CoX12, wherein X1 represents halogen, a sulfate radical, a perchlorate radical, a hexafluorophosphate radical, a hexafluoroantimonate radical, a tetrafluoroborate radical, a trifluoromethanesulfonate radical or a tetra(pentafluorophenyl)borate radical. The cobalt complex can be used in the selective catalysis of the transfer hydrogenation reaction ofthe cyano group to obtain a primary amine compound, a secondary amine compound and a tertiary amine compound, the primary amine compound, the secondary amine compound and the tertiary amine compoundare important intermediates in a series of subsequent functionalizing reactions, and the cobalt complex has a very high catalysis activity, and has great research values and a great application prospect.
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Paragraph 0165-0167; 0170
(2018/05/07)
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- An improved and one-pot procedure to the synthesis of symmetric amines by domino reactions of 5-methyl-1,3,4-thiadiazole-2-amine, a new nitrogen atom donor, and alkyl halides
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Abstract: A new one-pot method has been introduced in this work for the synthesis of symmetrical primary, secondary, and tertiary alkyl amines from alkyl halides and 5-methyl-1,3,4-thiadiazole-2-amine as a nitrogen-transfer reagent. In this method, all three types of amines have been successfully prepared after changing the ratio of substrates and base control. In addition to the introduction of a new nitrogen-transfer reagent, other important features of this work include normal atmospheric conditions and excellent yields under mild reaction conditions.
- Soleiman-Beigi, Mohammad,Mohammadi, Fariba
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p. 2123 - 2128
(2017/10/26)
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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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- Mild and Selective Cobalt-Catalyzed Chemodivergent Transfer Hydrogenation of Nitriles
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Herein, we describe a selective cobalt-catalyzed chemodivergent transfer hydrogenation of nitriles to synthesize primary, secondary, and tertiary amines. The solvent effect plays a key role for the selectivity control. The general applicability of this procedure was highlighted by the synthesis of more than 70 amine products bearing various functional groups in high chemoselectivity. Moreover, this mild system achieved >2000 TONs (turnover numbers) for the transfer hydrogenation of nitriles.
- Shao, Zhihui,Fu, Shaomin,Wei, Mufeng,Zhou, Shaolin,Liu, Qiang
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supporting information
p. 14653 - 14657
(2016/11/23)
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- Cationic Iridium and Rhodium Complexes with C-N Chelating Primary Benzylic Amine Ligands as Potent Catalysts for Hydrogenation of Unsaturated Carbon-Nitrogen Bonds
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Cationic half-sandwich C-N chelating Ir and Rh complexes [Cp?M(NCCH3){2(N,C)-NH2CR2-2-C6H4}]+SbF6- (1a, M = Ir, R = CH3; 1b, M = Ir, R = C6H5; 2a, M = Rh, R = CH3; 2b, M = Rh, R = C6H5) are synthesized by AgSbF6-mediated halide abstraction from neutral azametallacycles derived from tritylamine or cumylamine and are fully characterized by NMR spectroscopy and X-ray crystallography. The treatment of the cationic complex 1b with H2 gas under ambient conditions in the presence of triethylamine in THF-d8 quantitatively yielded hydrido(amine) complex [Cp?Ir(H){2(N,C)-NH2C(C6H5)2-2-C6H4}] (4). The C-N chelating Ir complex shows a higher catalytic activity than an N-N chelating complex, [Cp?Ir(NCCH3)(Tscydn)]+SbF6- (3; Tscydn = N-(p-toluenesulfonyl)-1,2-cyclohexanediamime), that has been previously used for the asymmetric hydrogenation of acyclic imines. For example, the cationic Ir complex 1a promoted the hydrogenation of N-(1-phenylethylidene)benzylamine under 30 atm at 30 °C in the presence of excess AgSbF6 to produce the corresponding amine in 97% yield within 2 h. The cationic Rh complexes 2 serve as efficient catalysts for hydrogenative condensation of nitriles in the presence of AgSbF6, producing dibenzylamines selectively even at 60 °C.
- Sato, Yasuhiro,Kayaki, Yoshihito,Ikariya, Takao
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p. 1257 - 1264
(2016/06/01)
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- Cobalt-Catalyzed Synthesis of Aromatic, Aliphatic, and Cyclic Secondary Amines via a "hydrogen-Borrowing" Strategy
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The replacement of precious metals with inexpensive, less toxic, and earth-abundant elements in typical noble-metal-mediated organic transformations is a major goal in current synthetic chemistry and industries. The metal-catalyzed N-alkylation of amines with other amines through a "hydrogen-borrowing" principle represents a green and atom-economical reaction for the synthesis of secondary amines. However, catalysts developed thus far that are effective for this process remain quite scarce and are only limited to a few ruthenium and iridium complexes. In this work, we present a cobalt-catalyzed selective alkylation of amines with amines to synthesize a large variety of secondary amines. A range of amine substrates have been converted to the corresponding products through hetero- or homocoupling between amines. Cyclic sec-amines are also achieved from diamine precursors as rare examples.
- Yin, Zhiwei,Zeng, Haisu,Wu, Jing,Zheng, Shengping,Zhang, Guoqi
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p. 6546 - 6550
(2016/10/14)
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- Colloid and nanosized catalysts in organic synthesis: XIV. Reductive amination and amidation of carbonitriles catalyzed by nickel nanoparticles
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Hydrogenation of carbonitriles catalyzed by nickel nanoparticles in the presence of primary amines led to the predominant formation of unsymmetrical secondary amines. In the presence of secondary amines hydrogenation of nitrites provided enamines as main products. Hydrogenation of nitriles in the presence of formamide or acetamide afforded formyl or acetyl derivatives of primary amines.
- Popov, Yu. V.,Mokhov,Shcherbakova
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p. 798 - 805
(2016/06/13)
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- Colloid and nanosized catalysts in organic synthesis: XII. Hydrogenation of carbonitriles catalyzed by nickel nanoparticles
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Hydrogenation of carbonitriles catalyzed by nickel nanoparticles in isopropanol proceeds under atmospheric pressure of hydrogen within 6-15 h to yield mainly secondary amines. Hydrogenation of α-aminonitriles results in reductive decyanation. β-Aminonitriles undergo hydrogenolysis at the nitrogen-carbon bond.
- Mokhov,Popov,Shcherbakova
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p. 273 - 280
(2016/04/20)
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- Facile Synthesis and Isolation of Secondary Amines via a Sequential Titanium(IV)-Catalyzed Hydroamination and Palladium-Catalyzed Hydrogenation
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An atom economical and catalytic route for the synthesis of aryl- and alkyl-substituted secondary amines has been developed. Using a bis(amidate)bis(amido)titanium(IV) precatalyst, the hydroamination of terminal alkynes with a range of amines results in the selective formation of the anti-Markovnikov product. The crude enamine/imine mixtures are effectively hydrogenated using palladium on carbon (Pd/C) and H2 to afford the corresponding secondary amine in excellent yields. Simple work-up procedures allow for the isolation of pure compounds while avoiding purification via column chromatography.
- Lui, Erica K. J.,Schafer, Laurel L.
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supporting information
p. 713 - 718
(2016/03/09)
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- Selective hydrogenation of benzyl cyanide to 2-phenylethylamine over a Pd/Al2O3 catalyst promoted by synergistic effects of CO2 and water
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The selective hydrogenation of benzyl cyanide (BC) to the primary amine of 2-phenylethylamine (PEA) was investigated with a Pd/Al2O3 catalyst in different multiphase reaction media including n-hexane, water, and/or CO2. In neat n-hexane, the hydrogenation of BC occurs at a large rate but no PEA was formed and the secondary amine of N,N-bis(2-phenylethyl)amine (BPEA) was produced as the main product. The pressurization of n-hexane with CO2 decreased the rate of hydrogenation and the main product was BPEA. In this n-hexane-CO2 medium, the catalyst lost its activity during the reaction. When a similar volume of water was added to n-hexane, the rate of hydrogenation did not change so much but a small amount of the primary amine was detected to form in addition to the main product of BPEA. In contrast to these reaction media, a high PEA selectivity of >90% was obtained and no catalyst deactivation occurred in an n-hexane-water-CO2 medium. The rate of hydrogenation was smaller than that in neat n-hexane but comparable to those in n-hexane-water and n-hexane-CO2 media. Those results show that synergistic effects appear on the selective hydrogenation of BC to PEA when both water and CO2 are included in the reaction medium. Possible roles and actions of water and CO2 have been discussed on the basis of the results of hydrogenation runs under different conditions and in situ ambient and high pressure Fourier transform infrared spectroscopy measurements that give insights into molecular interactions of CO2 with reacting species.
- Bhosale, Ashvini,Yoshida, Hiroshi,Fujita, Shin-Ichiro,Arai, Masahiko
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p. 1299 - 1307
(2015/03/04)
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- Unexpected selectivity in ruthenium-catalyzed hydrosilylation of primary amides: Synthesis of secondary amines
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Selective ruthenium-catalyzed reductive coupling of primary amides under hydrosilylation conditions is achieved using an one pot procedure. Using 3 equiv. of phenylsilane and [RuCl2(mesitylene)]2 (1-2 mol%) as the catalyst at 100 °C under neat conditions, secondary symmetric amines were obtained in good yields and with high chemoselectivities. The Royal Society of Chemistry 2013.
- Li, Bin,Sortais, Jean-Baptiste,Darcel, Christophe
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supporting information
p. 3691 - 3693
(2013/05/21)
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- A bifunctional palladium/acid solid catalyst performs the direct synthesis of cyclohexylanilines and dicyclohexylamines from nitrobenzenes
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Nitroderivatives are transformed to cyclohexylanilines at room temperature in good yields and selectivity via a hydrogenation-amine coupling cascade reaction using Pd nanoparticles on carbon as a catalyst and a Broensted acid.
- Rubio-Marques, Paula,Leyva-Perez, Antonio,Corma, Avelino
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supporting information
p. 8160 - 8162
(2013/09/12)
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- Pt/C catalysed direct reductive amination of nitriles with primary amines in a continuous flow multichannel microreactor
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Aliphatic and aromatic secondary amines were synthesised selectively by one pot reductive amination of nitriles with primary amines using Pt/C (3% by weight) catalyst in a continuous flow multichannel microreactor. Molecular hydrogen was used as a clean reducing agent at moderate reaction conditions. The Royal Society of Chemistry 2013.
- Sharma, Sumeet K.,Lynch, James,Sobolewska, Anna M.,Plucinski, Pawel,Watson, Robert J.,Williams, Jonathan M. J.
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- Development of a general non-noble metal catalyst for the benign amination of alcohols with amines and ammonia
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The N-alkylation of amines or ammonia with alcohols is a valuable route for the synthesis of N-alkyl amines. However, as a potentially clean and economic choice for N-alkyl amine synthesis, non-noble metal catalysts with high activity and good selectivity are rarely reported. Normally, they are severely limited due to low activity and poor generality. Herein, a simple NiCuFeOx catalyst was designed and prepared for the N-alkylation of ammonia or amines with alcohol or primary amines. N-alkyl amines with various structures were successfully synthesized in moderate to excellent yields in the absence of organic ligands and bases. Typically, primary amines could be efficiently transformed into secondary amines and N-heterocyclic compounds, and secondary amines could be N-alkylated to synthesize tertiary amines. Note that primary and secondary amines could be produced through a one-pot reaction of ammonia and alcohols. In addition to excellent catalytic performance, the catalyst itself possesses outstanding superiority, that is, it is air and moisture stable. Moreover, the magnetic property of this catalyst makes it easily separable from the reaction mixture and it could be recovered and reused for several runs without obvious deactivation. Copyright
- Cui, Xinjiang,Dai, Xingchao,Deng, Youquan,Shi, Feng
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supporting information
p. 3665 - 3675
(2013/03/29)
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- Heavier alkaline earth catalysts for the intermolecular hydroamination of vinylarenes, dienes, and alkynes
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The heavier group 2 complexes [M{N(SiMe3)2} 2]2(1, M = Ca; 2, M = Sr) and [M{CH(SiMe3) 2}2(THF)2] (3, M = Ca; 4, M = Sr) are shown to be effective precatalysts for the intermolecular hydroamination of vinyl arenes and dienes under mild conditions. Initial studies revealed that the amide precatalysts, 1 and 2, while compromised in terms of absolute activity by a tendency toward transaminative behavior, offer greater stability toward polymerization/oligomerization side reactions. In every case the strontium species, 2 and 4, were found to outperform their calcium congeners. Reactions of piperidine with para-substituted styrenes are indicative of rate-determining alkene insertion in the catalytic cycle while the ease of addition of secondary cyclic amines was found to be dependent on ring size and reasoned to be a consequence of varying amine nucleophilicity. Hydroamination of conjugated dienes yielded isomeric products via η3-allyl intermediates and their relative distributions were explained through stereoelectronic considerations. The ability to carry out the hydroamination of internal alkynes was found to be dramatically dependent upon the identity of the alkyne substituents while reactions employing terminal alkynes resulted in the precipitation of insoluble and unreactive group 2 acetylides. The rate law for styrene hydroamination with piperidine catalyzed by [Sr{N(SiMe3) 2}2]2 was deduced to be first order in [amine] and [alkene] and second order in [catalyst], while large kinetic isotope effects and group 2 element-dependent ΔS? values implicated the formation of an amine-assisted rate-determining alkene insertion transition state in which there is a considerable entropic advantage associated with use of the larger strontium center.
- Brinkmann, Christine,Barrett, Anthony G. M.,Hill, Michael S.,Procopiou, Panayiotis A.
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supporting information; experimental part
p. 2193 - 2207
(2012/03/10)
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- Homogeneous hydrogenations of nitriles catalyzed by rhenium complexes
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Rhenium(I) nitrosyl complexes bearing large bite angle diphosphines efficiently catalyze the hydrogenation of nitriles to the corresponding symmetrical secondary amines. Copyright
- Rajesh, Kunjanpillai,Dudle, Balz,Blacque, Olivier,Berke, Heinz
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scheme or table
p. 1479 - 1484
(2011/08/05)
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- Pt-Sn/γ-Al2O3-catalyzed highly efficient direct synthesis of secondary and tertiary amines and imines
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Versatile syntheses of secondary and tertiary amines by highly efficient direct N-alkylation of primary and secondary amines with alcohols or by deaminative self-coupling of primary amines have been successfully realized by means of a heterogeneous bimetallic Pt-Sn/γ-Al2O3 catalyst (0.5 wt % Pt, Pt/Sn molar ratio=1:3) through a borrowing-hydrogen strategy. In the presence of oxygen, imines were also efficiently prepared from the tandem reactions of amines with alcohols or between two primary amines. The proposed mechanism reveals that an alcohol or amine substrate is initially dehydrogenated to an aldehyde/ketone or NH-imine with concomitant formation of a [PtSn] hydride. Condensation of the aldehyde/ketone species or deamination of the NH-imine intermediate with another molecule of amine forms an N-substituted imine which is then reduced to a new amine product by the in-situ generated [PtSn] hydride under a nitrogen atmosphere or remains unchanged as the final product under an oxygen atmosphere. The Pt-Sn/γ-Al2O 3 catalyst can be easily recycled without Pt metal leaching and has exhibited very high catalytic activity toward a wide range of amine and alcohol substrates, which suggests potential for application in the direct production of secondary and tertiary amines and N-substituted imines.
- He, Wei,Wang, Liandi,Sun, Chenglin,Wu, Kaikai,He, Songbo,Chen, Jiping,Wu, Ping,Yu, Zhengkun
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experimental part
p. 13308 - 13317
(2012/02/02)
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- Catalysts based on filamentous carbon in the hydrogenation of aromatic compounds
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In order to extend the area of application of the base catalytic system metal-filamentous carbon, the catalytic properties of Ni-filamentous carbon catalysts have been tested in the hydrogenation of aromatic compounds (benzene, benzyl cyanide, benzophenon
- Zaitseva,Goidin,Molchanov,Chesnokov,Buyanov,Utkin
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experimental part
p. 770 - 773
(2011/11/30)
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- Synthesis and evaluation of oryzalin analogs against Toxoplasma gondii
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The synthesis and evaluation of 20 dinitroanilines and related compounds against the obligate intracellular parasite Toxoplasma gondii is reported. Using in vitro cultures of parasites in human fibroblasts, we determined that most of these compounds selectively disrupted Toxoplasma microtubules, and several displayed sub-micromolar potency against the parasite. The most potent compound was N1,N1-dipropyl-2,6-dinitro-4-(trifluoromethyl)-1,3- benzenediamine (18b), which displayed an IC50 value of 36 nM against intracellular T. gondii. Based on these data and another recent report [Ma, C.; Tran, J.; Gu, F.; Ochoa, R.; Li, C.; Sept, D.; Werbovetz, K.; Morrissette, N. Antimicrob. Agents Chemother. 2010, 54, 1453], an antimitotic structure-activity relationship for dinitroanilines versus Toxoplasma is presented.
- Endeshaw, Molla M.,Li, Catherine,Leon, Jessica De,Yao, Ni,Latibeaudiere, Kirk,Premalatha, Kokku,Morrissette, Naomi,Werbovetz, Karl A.
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scheme or table
p. 5179 - 5183
(2010/10/03)
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- A new atom-economical and selective synthesis of secondary and tertiary alkylamines by means of Cp*Iridium complex catalyzed multiple N-alkylation of ammonium salts with alcohols without solvent
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A new atom-economical and selective synthetic method for secondary and tertiary alkylamines has been achieved by means of (pentamethylcyclopentadienyl) iridium (Cp*Ir) complex catalyzed multiple N-alkylations of ammonium salts with primary and secondary alcohols without solvent. Georg Thieme Verlag Stuttgart.
- Yamaguchi, Ryohei,Mingwen, Zhu,Kawagoe, Shoko,Asai, Chiho,Fujita, Ken-Ichi
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experimental part
p. 1220 - 1223
(2009/12/04)
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- Gold catalysts open a new general chemoselective route to synthesize oximes by hydrogenation of α,β-unsaturated nitrocompounds with H 2
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The unprecedented chemoselective reduction of α,β-unsaturated nitroalkenes to oximes using hydrogen has been achieved with gold nanoparticles supported on TiO2. In contrast to the excellent catalytic performance of gold, related palladium and platinum catalysts are unselective, leading to the reduction of C=C double bond as well as the reduction of the NO2 to NH2. The selectivity of Au/TiO2 for the formation of oximes opens the way for the general use of the Henry reaction in organic synthesis. Copyright
- Corma, Avelino,Serna, Pedro,Garcia, Hermenegildo
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p. 6358 - 6359
(2008/02/09)
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- 2,3,4,9-TETRAHYDRO-1H-CARBAZOLE DERIVATIVES AS CRTH2 RECEPTOR ANTAGONISTS
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The invention relates to novel tetrahydro-lH-carbazole derivatives and their use as active ingredients in the preparation of pharmaceutical compositions. The invention also concerns related aspects including processes for the preparation of the compounds, pharmaceutical compositions containing one or more of those compounds and methods of treatment comprising administration of said compounds to patients.
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Page/Page column 52
(2008/06/13)
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- Organic compounds
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Novel compounds that inhibit the binding of the Smac protein to Inhibitor of Apoptosis Proteins (IAPs) of the formula I
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Page/Page column 22-23
(2008/06/13)
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- INDOL-1-YL-ACETIC ACID DERIVATIVES
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The invention relates to indol-1-yl-acetic acid derivatives and their use as active ingredients in the preparation of pharmaceutical compositions. The invention also concerns related aspects including processes for the preparation of the compounds, pharmaceutical compositions containing one or more of those compounds and methods of treatment comprising administration of said compounds.
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Page/Page column 70-71
(2010/02/14)
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- The facile preparation of primary and secondary amines via an improved Fukuyama-Mitsunobu procedure. Application to the synthesis of a lung-targeted gene delivery agent
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An efficient modification of the Fukuyama-Mitsunobu procedure has been developed whereby primary or secondary amines can be synthesized from alkyl alcohols and the corresponding nosyl-protected/activated amine. Most importantly, the use of the DTBAD and diphenylpyridinylphosphine, as Mitsunobu reagents, generates reaction by-products that can be easily removed, providing a remarkably clean product mixture. This improved technique was implemented in the synthesis of a complex lipopeptide designed to target α 9β1-integrin proteins predominant on upper airway epithelial cells. The Royal Society of Chemistry 2005.
- Guisado, Cristina,Waterhouse, Jodie E.,Price, Wayne S.,Jorgensen, Michael R.,Miller, Andrew D.
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p. 1049 - 1057
(2007/10/03)
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- Microwave-assisted synthesis of primary amine HX salts from halides and 7 M ammonia in methanol
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The atom economical synthesis of hydrogen halide salts of primary amines, directly from the corresponding halides, avoids the production of significant amounts of secondary amine side products, and requires only evaporation of the solvent to access the products in yields generally greater than 90%. The procedure uses microwave irradiation in 7 M ammonia in methanol (Aldrich) at 130°C from 0.5 to 2.5h and works on a variety of alkyl halides, as well as mesylates and tosylates. Benzylamines are obtained from benzyl halides without significant amounts of the secondary amine side products that result without microwave heating. Direct isolation of even highly volatile primary amines as their hydrogen halide salts makes the method ideal for use in parallel synthesis.
- Saulnier, Mark G.,Zimmermann, Kurt,Struzynski, Charles P.,Sang, Xiaopeng,Velaparthi, Upender,Wittman, Mark,Frennesson, David B.
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p. 397 - 399
(2007/10/03)
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- Rapid reduction of nitriles to primary amines with nickel boride at ambient temperature
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Reduction of a variety of nitriles to their corresponding primary amines can be achieved with nickel boride generated in situ in dry ethanol at ambient temperature. The reductions are very rapid and chemoselective.
- Khurana, Jitender M.,Kukreja, Gagan
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p. 1265 - 1269
(2007/10/03)
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- Convenient synthesis of protected primary amines form nitriles
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Investigations into the use of nickel chloride and sodium borohydride for the reduction of nitriles showed the secondary amine dimers to be the major products under normal conditions. The addition of a suitable trapping agent, such as di-tert-butyl dicarbonate, allowed the isolation of the protected primary amines. (C) 2000 Elsevier Science Ltd.
- Caddick, Stephen,De K. Haynes, Alexandra K.,Judd, Duncan B.,Williams, Meredith R.V.
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p. 3513 - 3516
(2007/10/03)
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- Studies of Reduction with Dimethoxyborane-Transition Metal Salt Systems. I. Reduction of Nitriles, Aldehydes and Ketones with Dimethoxyborane-Transition Metal Salt Systems
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The reduction of a variety of functional groups with new dimethoxyborane-transition metal salt systems was investigated.The dimethoxyborane-cobaltous chloride system reduced nitriles and aldehydes under mild conditions in good yields, and the dimethoxyborane-nickelous chloride system similarly reduced nitriles, aldehydes, olefin and ketones.The other functional groups tested were unaffected by these systems.Keywords reduction; nitrile; aldehyde; ketone; dimethoxyborane; transition metal salt; dimethoxyborane-cobaltous chloride system; dimethoxyborane-nickelous chloride system
- Nose, Atsuko,Kudo, Tadahiro
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p. 808 - 810
(2007/10/02)
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- The Chemistry of N-Substituted Benzotriazoles. Part 14. Novel Routes to Secondary and Tertiary Amines and to N,N-Disubstituted Hydroxylamines
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Tertiary amines of types R4R3CHNR1R2 (2), (R2CH2)2NR1 (10) and 11, or (R2CH2)3N (12), secondary amines of type (R2CH2)2NH (8), and N,N-disubstituted hydroxylamines of type (R2CH2)2NOH (9), are prepared in high yield by the action of Grignard reagents or sodium borohydride on easily available N,N-dialkyl-N-amines (1) or tris(benzotriazolylmethyl)amine (7), on bis(benzotriazolylmethyl)amines (3), (5), and (6), and on N,N-bis(benzotriazolylmethyl)hydroxylamine (4), respectively.
- Katritzky, Alan R.,Yannakopoulou, Konstantina,Lue, Ping,Rasala, Danuta,Urogdi, Laszlo
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p. 225 - 233
(2007/10/02)
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- STUDIES OF REDUCTION WITH THE DIBORANE-TRANSITION METAL SALT SYSTEM
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The reduction of a variety of functional groups with the new diborane-nickelous chloride system was systematically investigated.This system reduced aromatic nitro compounds to the corresponding primary amines under mild conditions in good yields.However, ketone, aldehyde, carboxylic acid, ester, amide and olefin moieties were unaffected by this system.Thenitro group in aromatic nitro compounds bearing a ketone, aldehyde, ester, amide or nitrile functionality was selectively reduced with this system to give the corresponding primary amines in good yields.KEYWORDS - selective reduction; aromatic nitro compound; diborane; nickelous chloride; diborane-transition metal salt system; aromatic primary amine.
- Nose, Atsuko,Kudo, Tadahiro
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p. 3905 - 3909
(2007/10/02)
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- FORMATION OF SULPHUR COMPOUNDS DURING THE HYDRODENITROGENATION OF ANILINE, CYCLOHEXYLAMINE, BENZYLAMINE, AND 2-PHENYLETHYLAMINE ON A NICKEL-TUNGSTEN CATALYST IN THE PRESENCE OF HYDROGEN SULPHIDE
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Hydrodenitrogenations of aniline, cyclohexylamine, benzylamine, and 2-phenylethylamine were performed on a sulphided nickel-tungsten catalyst at 300 deg C in an autoclave filled with hydrogen in the absence and in the presence of hydrogen sulphide.Due to the presence of hydrogen sulphide the degree of conversion increased from 0.9 to 3,6percent for aniline and from 72 to 99percent for benzylamine, and the fraction of neutral substances increased from 2.4 to 7percent for cyclohexylamine and from 5.0 to 8.9percent for 2-phenylethylamine.The neutral fractions contained cyclohexanethiol, thiobenzamide, 2-phenylethanethiol, and other sulphur compounds giving evidence that the increased degree of conversion of the amines was due to the hydrogen sulphide taking direct part in the chemical reaction.
- Cerny, Mirko,Trka, Antonin
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p. 2387 - 2392
(2007/10/02)
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- DEACYLATION OF ALKYL CARBAMATES: SELECTIVE DEPROTECTION OF SECONDARY AMINES
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Selective deacylation of N,N-disubstituted alkyl carbamates over N-monosubstituted alkyl carbamates can be acheived in excellent yield by the addition of three equivalents of methyl lithium.
- Sawyer, J. Scott,Narayanan, Bikshandarkoil A.
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p. 135 - 138
(2007/10/02)
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