- Iridium-Catalyzed Alkylation of Amine and Nitrobenzene with Alcohol to Tertiary Amine under Base- and Solvent-Free Conditions
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Herein, an efficient and green method for the selective synthesis of tertiary amines has been developed that involves iridium-catalyzed alkylation of various primary amines with aromatic or aliphatic alcohols. Notably, the catalytic protocol enables this transformation in the absence of additional base and solvent. Furthermore, the alkylation of nitrobenzene with primary alcohol to tertiary amine has also been achieved by the same catalytic system. Deuterium-labeling experiments and a series of control experiments were conducted, and the results suggested that an intermolecular borrowing hydrogen pathway might exist in the alkylation process.
- Li, Chao,Wan, Ke-Feng,Guo, Fu-Ya,Wu, Qian-Hui,Yuan, Mao-Lin,Li, Rui-Xiang,Fu, Hai-Yan,Zheng, Xue-Li,Chen, Hua
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p. 2158 - 2168
(2019/05/16)
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- Copper-catalyzed electrophilic amination using: N -methoxyamines
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Copper-catalyzed electrophilic amination of a triarylboroxin using an N-methoxyamine to give quick access to a variety of anilines was reported. The reaction was especially useful for syntheses of functionalized anilines when combined with our previously reported nucleophilic addition to N-methoxyamides.
- Fukami, Yutaro,Wada, Takamasa,Meguro, Tatsuhiko,Chida, Noritaka,Sato, Takaaki
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supporting information
p. 5486 - 5489
(2016/07/06)
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- Method of producing higher amine (by machine translation)
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PROBLEM TO BE SOLVED: To provide a method of producing a secondary or tertiary higher amine. SOLUTION: The method of producing a higher amine comprises allowing a primary or secondary amine to react with an alcohol in the presence of at least one species of hydrogen halide selected from hydrogen chloride, hydrogen bromide and hydrogen iodide, or in the presence of a compound capable of producing a hydrogen halide (such as 1,3,5-triazo-2,4,6-triphosphorine-2,2,4,4,6,6-chloride). If the raw material amine is a primary amine, a secondary higher amine and a tertiary higher amine can be produced. If the raw material amine is a secondary amine, a tertiary higher amine can be produced. COPYRIGHT: (C)2012,JPO&INPIT
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Paragraph 0048; 0091; 0104
(2016/10/08)
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- SiO2-Cu2O: An efficient and recyclable heterogeneous catalyst for N-benzylation of primary and secondary amines
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A mild, effective, and selective procedure is reported for the mono N-benzylation and N,N-dibenzylation of primary amines as well as mono N-benzylation of secondary amines using silica-supported copper(I) oxide in water. The silica-supported Cu2O was generated in situ by the reaction of Fehling solution and glucose at 100 C onto activated silica. The catalyst was filtered, washed with water, and oven-dried, and was characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy, and atomic absorption spectroscopy. The prepared Cu2O-SiO2 was found to be thermally stable up to 325 C. The copper was uniformly distributed onto the surface of the silica, and the mean particle diameter was 7 nm. The catalyst served as a selective heterogenous catalyst for the N-benzylation of primary and secondary amines. The catalyst is recyclable and was used effectively upto fifth run without a significant loss of catalytic activity. Various reaction solvents including water, acetonitrile, and toluene were screened for N-benzylation of amines, and the success of the aqueous system highlights the low environmental impact of the procedure.
- Gupta, Manjulla,Paul, Satya,Gupta, Rajive
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p. 444 - 450
(2014/04/03)
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- N-alkylation of amines by homogeneous ruthenium complexes in the presence of free diphosphines
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Chemoselective N-alkylation of amines by ruthenium complexes in the presence of free diphosphine ligands under mild conditions is described. Octyl amine and aniline were chosen as aliphatic and aromatic amines to investigate the effect of different phosphines, reaction times, and temperature on conversion, as well as selectivity towards related secondary and tertiary amines. After optimization of the reaction conditions, this catalytic system was used for N-alkylation of other amines and has shown moderate to very good yields. The reaction products were monitored by GC-MS. The crystal structure of [Ru(NO3)2CO(PPh3)2] with a monodentate and a bidentate nitrate was determined by X-ray crystallographic analysis.
- Tamaddoni Jahromi, Bahareh,Kharat, Ali Nemati
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p. 3498 - 3508
(2014/01/06)
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- Copper-catalyzed electrophilic amination of arylsilanes with hydroxylamines
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A copper-catalyzed electrophilic amination of aryl[(2-hydroxymethyl)phenyl] dimethylsilanes with O-acylated hydroxylamines has been developed to afford the corresponding anilines in good yields. The catalytic reaction proceeds very smoothly under mild conditions and tolerates a wide range of functional groups.
- Miki, Yuya,Hirano, Koji,Satoh, Tetsuya,Miura, Masahiro
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supporting information
p. 172 - 175
(2013/03/28)
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- Transition-metal-free electrophilic amination of arylboroxines
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A transition-metal-free strategy to construct C(sp2)-N bonds using arylboroxines and O-benzoyl hydroxylamines as coupling partners has been developed. This transformation provides a useful method to access various aromatic amines.
- Xiao, Qing,Tian, Leiming,Tan, Renchang,Xia, Ying,Qiu, Di,Zhang, Yan,Wang, Jianbo
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p. 4230 - 4233
(2012/09/22)
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- Fe2O3-supported nano-gold catalyzed one-pot synthesis of N-alkylated anilines from nitroarenes and alcohols
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Here, we show the one-step synthesis of N-alkylated anilines from nitrobenzenes and alcohols catalyzed by nano-gold catalyst. The yields to N-alkylated anilines were ~90% under mild conditions. The mechanism of this reaction was explored. It shows promise for clean and simple synthesis of N-alkylated anilines.
- Peng, Qiling,Zhang, Yan,Shi, Feng,Deng, Youquan
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supporting information; experimental part
p. 6476 - 6478
(2011/06/28)
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- Selective N-alkylation of amines with alcohols by using non-metal-based acid-base cooperative catalysis
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Learning to cooperate: A straightforward method for the selective N-mono- and dialkylation of amines with alcohols by means of non-metal-based catalysis promoted by TAPC is reported (see scheme). Selectivity of the N-mono- and dialkylation, substrate scope and functional-group tolerance are highlighted with respect to each amine (1° and 2°; aromatic and aliphatic) and alcohol (1°, 2° and 3°; benzylic and aliphatic) component. Copyright
- Du, Ya,Oishi, Shunsuke,Saito, Susumu
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supporting information; experimental part
p. 12262 - 12267
(2011/11/29)
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- Ruthenium-catalyzed tertiary amine formation from nitroarenes and alcohols
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A highly selective ruthenium-catalyzed C-N bond formation was developed by using the hydrogen-borrowing strategy. Various tertiary amines were obtained efficiently from nitroarenes and primary alcohols. The reaction tolerates a wide range of functionalities. A tentative mechanism was proposed for this direct amination reaction of alcohols with nitroarenes.
- Feng, Chao,Liu, Yong,Peng, Shengming,Shuai, Qi,Deng, Guojun,Li, Chao-Jun
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supporting information; experimental part
p. 4888 - 4891
(2010/12/25)
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- Transition metal-free amination of aryl halides-A simple and reliable method for the efficient and high-yielding synthesis of N-arylated amines
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A simple and reliable reaction protocol for the clean, fast, and high-yielding synthesis of various N-arylated amines derived from reactions of aryl halides with various (also sterically hindered) amines under transition metal-free reaction conditions is presented. Dioxane and KN(Si(CH3)3)2 were found to be the ideal solvent and base for this transformation. The conversion rates and yields observed are excellent and in the majority of the reactions performed significantly higher than that obtained in their catalyzed versions. Furthermore, the selective synthesis of 6-halopyridin-2-amines and asymmetric pyridine-2,6-diamines (derived from consecutive reactions of 2,6-dibromopyridine and 2,6-dichloropyridine, respectively, with different amines) is possible in almost quantitative yields (relative to 2,6-dihalopyridine) within very short reaction times. Purification of the 6-halopyridin-2-amine intermediates is not necessary, allowing the synthesis of pyridine-2,6-diamines in 'one-pot'. However, catalysts are in many cases not required to efficiently and selectively couple aryl halides with amines, making transition metal-free versions of the Buchwald-Hartwig reaction extremely attractive for the synthesis of N-arylated amines with substrates containing substituents on the aryl halide, which either promote regioselectivity and/or do not require regioselective aminations.
- Bolliger, Jeanne L.,Frech, Christian M.
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supporting information; experimental part
p. 1180 - 1187
(2009/04/10)
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- Aqueous-mediated N-alkylation of amines
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Direct N-alkylation of primary amines to secondary/tertiary amines and of secondary amines to tertiary amines has been achieved in excellent yields by employing alkyl, benzylic and allylic halides in the presence of NaHCO 3 in an aqueous medium at an elevated temperature. Amines of different stereoelectronic nature react with ease with different halides. The selective formation of secondary amines and the formation of three different substituted tertiary amines are some of the interesting features of this methodology. Reaction in an aqueous medium, operationally convenient conditions, excellent yields and innocuous byproducts, and the absence of transition-metal catalysts, expensive bases, solid supports and the formation of undesired quaternary ammonium salts makes this method a green chemical process. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
- Singh, Chingakham B.,Kavala, Veerababurao,Samal, Akshaya K.,Patel, Bhisma K.
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p. 1369 - 1377
(2008/09/17)
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