- Manganese Catalyzed Hydrogenation of Azo (N=N) Bonds to Amines
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We report the first example of homogeneously catalyzed hydrogenation of the N=N bond of azo compounds using a complex of an earth-abundant-metal. The hydrogenation reaction is catalyzed by a manganese pincer complex, proceeds under mild conditions, and yields amines, which makes this methodology a sustainable alternative route for the conversion of azo compounds. A plausible mechanism involving metal-ligand cooperation and hydrazine intermediacy is proposed based on mechanistic studies. (Figure presented.).
- Ben-David, Yehoshoa,Das, Uttam Kumar,Diskin-Posner, Yael,Kar, Sayan,Milstein, David
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supporting information
p. 3744 - 3749
(2021/07/09)
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- Methoxy aniline compound and synthesis method thereof
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The invention mainly relates to a preparation method of anisidine. According to the technical scheme, under the promotion of the photocatalyst and blue light, in the argon atmosphere, nitro compounds and methanol generate methoxyaniline, wherein products and additional products with stable molecular structures and excellent chemical properties are prepared, wherein a photocatalyst and a blue light source are used in the method, and a new path is provided for synthesis of methoxyaniline compounds. The method has the characteristics of mild reaction conditions, simple reaction system, less reaction equipment, simplicity and convenience in experimental operation and the like. The methoxyaniline derivative and the synthetic method thereof can be applied to a plurality of industrial production fields of dyes, pesticides, medicines, rubber additives and the like. The method is particularly suitable for scientific research, development and utilization of efficient and selective synthesis of methoxyaniline compounds by a one-pot method.
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Paragraph 0027; 0030-0032; 0041-0042
(2021/05/19)
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- Deacetylative Amination of Acetyl Arenes and Alkanes with C-C Bond Cleavage
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The Br?nsted acid-catalyzed synthesis of primary amines from acetyl arenes and alkanes with C-C bond cleavage is described. Although the conversion from an acetyl group to amine has traditionally required multiple steps, the method described herein, which uses an oxime reagent as an amino group source, achieves the transformation directly via domino transoximation/Beckmann rearrangement/Pinner reaction. The method was also applied to the synthesis of γ-aminobutyric acids, such as baclophen and rolipram.
- Hyodo, Kengo,Hasegawa, Genna,Maki, Hiroya,Uchida, Kingo
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supporting information
p. 2818 - 2822
(2019/04/25)
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- Cu(II)-Mediated N-H and N-Alkyl Aryl Amination and Olefin Aziridination
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Cu(II)-mediated direct NH2 and NH alkyl aryl aminations and olefin aziridinations are described. These room-temperature, one-pot, environmentally friendly procedures replace costly Rh2 catalysts and, in some instances, display important differences with comparable Rh2- and Fe-supported reactions.
- Munnuri, Sailu,Anugu, Raghunath Reddy,Falck, John R.
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supporting information
p. 1926 - 1929
(2019/03/11)
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- Selective synthesis of mono- and di-methylated amines using methanol and sodium azide as C1 and N1 sources
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A Ru(ii) complex mediated synthesis of various N,N-dimethyl and N-monomethyl amines from organic azides using methanol as a methylating agent is reported. This methodology was successfully applied for a one-pot reaction of bromide derivatives and sodium azide in methanol. Notably, by controlling the reaction time several N-monomethylated and N,N-dimethylated amines were synthesized selectively. The practical applicability of this tandem process was revealed by preparative scale reactions with different organic azides and synthesis of an anti-vertigo drug betahistine. Several kinetic experiments and DFT studies were carried out to understand the mechanism of this transformation.
- Chakrabarti, Kaushik,Mishra, Anju,Panja, Dibyajyoti,Paul, Bhaskar,Kundu, Sabuj
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supporting information
p. 3339 - 3345
(2018/07/29)
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- Fe-Catalyzed Amination of (Hetero)Arenes with a Redox-Active Aminating Reagent under Mild Conditions
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A novel and efficient Fe-catalyzed direct C?H amination (NH2) of arenes is reported using a new redox-active aminating reagent. The reaction is simple, and can be performed under air, mild, and redox-neutral conditions. This protocol has a broad substrate scope and could be used in the late-stage modification of bioactive compounds. Mechanistic studies demonstrate that a radical pathway could be involved in this transformation.
- Liu, Jianzhong,Wu, Kai,Shen, Tao,Liang, Yujie,Zou, Miancheng,Zhu, Yuchao,Li, Xinwei,Li, Xinyao,Jiao, Ning
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supporting information
p. 563 - 567
(2017/01/18)
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- Secondary amides as hydrogen atom transfer promoters for reactions of samarium diiodide
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Two secondary amides (N-methylacetamide and 2-pyrrolidinone) were used as additives with SmI2 in THF to estimate the extent of N-H bond weakening upon coordination. Mechanistic and synthetic studies demonstrate significant bond-weakening, providing a reagent system capable of reducing a range of substrates through formal hydrogen atom transfer.
- Chciuk, Tesia V.,Li, Anna M.,Vazquez-Lopez, Andres,Anderson, William R.,Flowers, Robert A.
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supporting information
p. 290 - 293
(2017/11/27)
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- Transition-metal-free access to primary anilines from boronic acids and a common +NH2 equivalent
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Diversely substituted anilines are prepared by treatment of functionalized arylboronic acids with a common, inexpensive source of electrophilic nitrogen (H2N-OSO3H, HSA) under basic aqueous conditions. Electron-rich substrates are found to be the most reactive by this method. However, even moderately electron-poor substrates are well tolerated under the room temperature conditions. Sterically hindered substrates appear to be equally effective compared to unhindered ones. Highly electron-deficient substrates afford product in very low yields at room temperature, but moderate to good yields are obtained at refluxing temperatures. Our method is also amenable to electrophilic amination of several common boronic acid derivatives (e.g., pinacol esters). We demonstrate that it can be combined with metal-halogen exchange reactions or a variety of directed ortho metalation protocols in a "one-pot" sequence for the synthesis of aromatic amines with unique substitution patterns. DFT studies, in combination with experimental results, suggest that the reaction occurs via base-mediated activation of HSA, followed by 1,2 aryl B-N migration. This mode of activation appears to be critical for the success of the reaction and allows, for the first time, a general, electrophilic amination of boronic acids at ambient temperature.
- Voth, Samantha,Hollett, Joshua W.,Mccubbin, J. Adam
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p. 2545 - 2553
(2015/03/18)
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- Microwave-assisted protection of primary amines as 2,5-dimethylpyrroles and their orthogonal deprotection
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Primary amines can be readily doubly protected as N-substituted 2,5-dimethylpyrroles. Although this protecting group is stable toward strong bases and nucleophiles, long reaction times are required for both the protection and deprotection steps, generally resulting in low deprotection yields. By employing microwave irradiation, protection and deprotection reaction times are dramatically reduced. Furthermore, deprotection with dilute hydrochloric acid in ethanol increases reaction yields. Diverse deprotection conditions have been developed in conjunction with microwave irradiation, so that protection as an N-substituted 2,5-dimethylpyrrole can be orthogonal to other standard amine protecting groups, such as tert-butyloxycarbonyl (Boc), carbobenzyloxy (Cbz), and 9-fluorenylmethyloxycarbonyl (Fmoc).
- Walia, Amit,Kang, Soosung,Silverman, Richard B
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p. 10931 - 10937
(2013/11/19)
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- Magnetically separable CuFe2O4 nanoparticles in PEG: A recyclable catalytic system for the amination of aryl iodides
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A recyclable catalytic system comprising magnetically separable CuFe 2O4 nanoparticles in a poly(ethylene glycol) medium has been established as an inexpensive, nontoxic, environmentally benign system for the amination of aryl iodides with aqueous ammonia. A wide variety of aryl iodides underwent amination to afford the corresponding aryl amines in moderate to good yields. The catalytic system was recycled five times with consistent activity. Georg Thieme Verlag Stuttgart . New York.
- Kumar, A. Suresh,Ramani,Sreedhar
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supporting information
p. 938 - 942
(2013/06/27)
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- Na4W10O32/ZrO2 nanocomposite prepared via a sol-gel route: A novel, green and recoverable photocatalyst for reductive cleavage of azobenzenes to amines with 2-propanol
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Sodium decatungstate-zirconia (Na4W10O32/ZrO2) nanocomposite was prepared through entrapment of Na4W10O32 into zirconia matrix by a sol-gel route. This new nanocomposite was characterized by means of X-ray diffraction (XRD), Fourier-transformed infrared spectroscopy (FT-IR), UV-vis spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and surface area measurement. The nanocomposite was used as a green and recyclable heterogeneous photocatalyst for rapid and efficient reductive cleavage of azobenzenes into their corresponding amines with 2-propanol as a hydrogen donor at room temperature under N2 atmosphere. The reductive cleavage occurs without hydrogenolysis or hydrogenation of reducible moieties, such as -NO2, -OH, -CH3, -OCH3, -COOH, -COCH3, halogen and -CN. The photocatalyst has been reused several times, without observable loss of activity and selectivity. According to the azobenzene reduction, the Na4W10O32/ZrO2 nanocomposite is more effective as a photocatalyst than pure Na4W10O32, showing that the nanocomposite approach could be an excellent choice to improve the photoactivity of POMs.
- Farhadi, Saeid,Sepahvand, Shahnaz
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experimental part
p. 75 - 84
(2010/06/15)
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- Synthesis of casimiroin and optimization of its quinone reductase 2 and aromatase inhibitory activities
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An efficient method has been developed to synthesize casimiroin (1), a component of the edible fruit of Casimiroa edulis, on a multigram scale in good overall yield. The route was versatile enough to provide an array of compound 1 analogues that were evaluated as QR2 and aromatase inhibitors. In addition, X-ray crystallography studies of QR2 in complex with compound 1 and one of its more potent analogues has provided insight into the mechanism of action of this new series of QR2 inhibitors. The initial biological investigations suggest that compound 1 and its analogues merit further investigation as potential chemopreventive or chemotherapeutic agents.
- Maiti, Arup,Reddy, P. V. Narasimha,Sturdy, Megan,Marler, Laura,Pegan, Scott D.,Mesecar, Andrew D.,Pezzuto, John M.,Cushman, Mark
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experimental part
p. 1873 - 1884
(2009/12/31)
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- CuI/4-hydro-L-proline as a more effective catalytic system for coupling of aryl bromides with N-boc hydrazine and aqueous ammonia
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(Chemical Equation Presented) CuI/4-hydroxy-L-proline-catalyzed coupling of aryl bromides and N-Boc hydrazine takes place in DMSO at 80°C to give N-aryl hydrazides. When aryl iodides are employed, this reaction completes at 50°C and no ligand is required. Under the catalysis of CuI/4-hydroxy-L- proline, the coupling reaction of aqueous ammonia with aryl bromides proceeds smoothly at 50°C to afford primary arylamines. In this case K 2CO3 is found as a better base than Cs2CO 3. These processes allow assembly of N-aryl hydrazides and primary arylamines that bear a wide range of functional groups including hydroxyl, amine, trifluoromethyl, ester, nitro, and ketone.
- Jiang, Liqin,Lu, Xu,Zhang, Hui,Jiang, Yongwen,Ma, Dawei
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experimental part
p. 4542 - 4546
(2009/09/25)
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- Cross-coupling of aryl/heteroaryl bromides with ammonia using a copper-carbene catalyst
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A variety of aryl and heteroaryl bromides were cross-coupled with ammonia in good to high yields in the presence of a copper-NHC catalyst. The Royal Society of Chemistry.
- Ntaganda, Rukundo,Dhudshia, Bhartesh,Macdonald, Charles L. B.,Thadani, Avinash N.
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supporting information; experimental part
p. 6200 - 6202
(2009/05/06)
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- Amination of arenes with N,N-dimethyl-2-imidazolidinone O-methoxyacetyloxime
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Treatment of nucleophilic arenes with N,N-dimethyl-2imidazolidinone O-methoxyacetyloxime and SnCl4 produced the corresponding N-arylimines, which were converted to anilines by hydrolysis with CsOH and to N-methylanilines by LiAlH4 reduction.
- Baldovini, Nicolas,Kitamura, Mitsuru,Narasaka, Koichi
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p. 548 - 549
(2007/10/03)
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- Synthesis of primary amines and N-methylamines by the electrophilic amination of Grignard reagents with 2-imidazolidinone O-sulfonyloxime
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2-Imidazolidinone O-sulfonyloxime reacts with various aryl and alkyl Grignard reagents as an electrophilic amination reagent, giving N-alkylated imines. The resulting imines are transformed to primary amines and N-methyl secondary amines by hydrolysis with CsOH and LiAlH4 reduction, respectively.
- Kitamura, Mitsuru,Chiba, Shunsuke,Narasaka, Koichi
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p. 1063 - 1070
(2007/10/03)
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- Atypical regioselectivity in the electrochemical reduction-nucleophilic substitution of 2-nitroanisole
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The electrochemical reduction-Bamberger substitution of 2-nitroanisole in 1 M H2SO4 yields predominantly 2,5-dimethoxyaniline, not the expected 2,4-isomer. The selectivity was found to be acid- and solvent-dependent, with lower acidity and less polar solvents favoring the formation of 2,4- dimethoxyaniline during galvanostatic electrolysis. A mechanistic working hypothesis involving an ortho-quinone monoimine dication is presented to direct further synthetic studies.
- Wang, Wendong,Wu, Guo-Zhang,Goekjian, Peter G.
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p. 1517 - 1520
(2007/10/03)
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- Synthesis of aromatic amines from electron-rich arenes and bis(2,2,2-trichloroethyl) azodicarboxylate
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Electron-rich arenes react with bis(2,2,2-trichloroethyl) azodicarboxylate in 3 M lithium perchlorate-diethylether or acetone solution to produce para-substituted aryl hydrazides in high yields. The corresponding aromatic amines are readily obtained by reducing the hydrazides with zinc in acetic acid.
- Zaltsgendler,Leblanc,Bernstein
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p. 2441 - 2444
(2007/10/02)
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- 3-amino-5-methyl-1H-pyrazole-4-carboxylic acids and esters thereof as anticonvulsants, muscle relaxants and anxiolytics
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A novel method of controlling epilepsy, muscle tension, muscular spasticity, and anxiety in living animal bodies by administering compounds of the formula: STR1 wherein: R1 is hydrogen, loweralkyl or a pharmaceutically acceptable cation; R2 and R3, same or different, are hydrogen, loweralkyl, aryl, cycloalkyl, loweralkenyl, 1-adamantyl, heterocyclicaminoalkyl, diloweralkylaminoloweralkyl, or R2 with R3 and adjacent nitrogen may form a heterocyclic ring structure; and the pharmaceutical acceptable acid salts, and tautomeric isomers thereof; and novel pharmaceutical compositions therefor are disclosed.
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- Direct Photoamination of Arenes with Ammonia and Primary Amines in the Presence of Electron Acceptors
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Direct photoamination of phenanthrene, 9-methoxyphenanthrene, anthracene, naphthalene, and several substituted naphthalenes with ammonia or primary amines in the presence of m-dicyanobenzene occurs to give aminated dihydroarenes in fairly good yields. m-Dimethoxybenzene and biphenyl are photoaminated in lower yields.A suggested mechanism for the photoamination involves the nucleophilic attack of ammonia and amines on aromatic cation radicals generated by photochemical electron transfer to m-dicyanobenzene.The present photoamination is applied to direct introduction of various functionalized primary amines containing the vinyl, cyano, hydroxy, acetylamino, and ethoxycarbonyl groups.
- Yasuda, Masahide,Yamashita, Toshiaki,Shima, Kensuke,Pac, Chyongjin
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p. 753 - 759
(2007/10/02)
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- SYNTHESIS OF 5-SUBSTITUTED 4-O-METHYL TETRAMATES
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4-Methoxy-Δ3-pyrrolin-2-ones (4-O-methyl tetramates) are alkylated at C-5 via a lithio-derivative; an N-substituent may be introduced either during or after heterocycle formation.
- Jones, Raymond C.F,Bates, Andrew D.
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p. 5285 - 5288
(2007/10/02)
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- Metal-containing polypropylene dyed with monoazo 1-aryl-3-alkyl-5-pyrazolones
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Metal-containing polypropylene fibers dyed with monoazo 1-aryl-3-alkyl-5-pyrazolone compounds of the structure: STR1 where R is hydrogen or lower alkoxy, R" is lower alkyl, X is hydrogen or halogen, and X' is hydrogen or halogen Are provided. The dyed metal-containing polypropylene fibers have bright yellowish hues of outstanding crock fastness, light fastness and fastness to dry cleaning solvents.
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