769-06-2Relevant articles and documents
B(C6F5)3-Catalyzed C-H Alkylation of N-Alkylamines Using Silicon Enolates without External Oxidant
Chan, Jessica Z.,Chang, Yejin,Wasa, Masayuki
supporting information, p. 984 - 988 (2019/02/14)
An efficient method for the coupling of N-alkylamines with silicon enolates to generate β-amino carbonyl compounds is disclosed. These reactions proceed by activation of α-amino C-H bonds by B(C6F5)3, which likely generate
Expedient Synthesis of N-Methyl- and N-Alkylamines by Reductive Amination using Reusable Cobalt Oxide Nanoparticles
Senthamarai, Thirusangumurugan,Murugesan, Kathiravan,Natte, Kishore,Kalevaru, Narayana V.,Neumann, Helfried,Kamer, Paul C. J.,Jagadeesh, Rajenahally V.
, p. 1235 - 1240 (2018/02/09)
N-Methyl- and N-alkylamines represent important fine and bulk chemicals that are extensively used in both academic research and industrial production. Notably, these structural motifs are found in a large number of life-science molecules and play vital roles in regulating their activities. Therefore, the development of convenient and cost-effective methods for the synthesis and functionalization of amines by using earth-abundant metal-based catalysts is of scientific interest. In this regard, herein we report an expedient reductive amination process for the selective synthesis of N-methylated and N-alkylated amines by using nitrogen-doped, graphene-activated nanoscale Co3O4-based catalysts. Starting from inexpensive and easily accessible nitroarenes or amines and aqueous formaldehyde or aldehydes in the presence of formic acid, this cost-efficient reductive amination protocol allows the synthesis of various N-methyl- and N-alkylamines, amino acid derivatives, and existing drug molecules.
Diverse catalytic reactivity of a dearomatized PN3P?-nickel hydride pincer complex towards CO2 reduction
Li, Huaifeng,Gon?alves, Théo P.,Zhao, Qianyi,Gong, Dirong,Lai, Zhiping,Wang, Zhixiang,Zheng, Junrong,Huang, Kuo-Wei
supporting information, p. 11395 - 11398 (2018/10/20)
A dearomatized PN3P?-nickel hydride complex has been prepared using an oxidative addition process. The first nickel-catalyzed hydrosilylation of CO2 to methanol has been achieved, with unprecedented turnover numbers. Selective methylation and formylation of amines with CO2 were demonstrated by such a PN3P?-nickel hydride complex, highlighting its versatile functions in CO2 reduction.
N, N -Dimethylation of nitrobenzenes with CO2 and water by electrocatalysis
Sun, Xiaofu,Zhu, Qinggong,Hu, Jiayin,Kang, Xinchen,Ma, Jun,Liu, Huizhen,Han, Buxing
, p. 5669 - 5674 (2017/08/01)
We have proposed a strategy for the synthesis of N,N-dimethylanilines from nitrobenzene and its derivatives, CO2, and water via an electrochemical reaction under ambient conditions. H+ generated from H2O was used as the hydrogen source. Pd/Co-N/carbon, in which the Pd nanoparticles were supported on Co-N/carbon, was designed and used as the electrocatalyst. It was found that the electrocatalyst was very efficient for the reaction in MeCN solution with 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Bmim]Tf2N) as the supporting electrolyte and 1-amino-methylphosphonic acid (AMPA) as the thermal co-catalyst. A series of control experiments showed that Pd/Co-N/carbon and AMPA cooperated very well in accelerating the reaction. This synthetic route has some obvious advantages, such as using CO2 and water as the reactants, ambient reaction conditions, and high yields of the desired products. This opens up a way to synthesize chemicals by the combination of an electrocatalyst and a thermal catalyst with organic compounds, CO2, and water as the reactants.
Selective formylation and methylation of amines using carbon dioxide and hydrosilane catalyzed by alkali-Metal carbonates
Fang, Chi,Lu, Chunlei,Liu, Muhua,Zhu, Yiling,Fu, Yao,Lin, Bo-Lin
, p. 7876 - 7881 (2018/05/23)
The formylation and methylation of amines with carbon dioxide and hydrosilanes are emerging yet important types of transformations for CO2. Catalytic methods effective for both reactions with wide substrate scopes are rare because of the difficulty in controlling the selectivity. Herein, we report that simple and readily available inorganic bases alkali-metal carbonates, especially cesium carbonatecatalyze both the formylation and methylation reactions efficiently under mild conditions. The selectivity can be conveniently controlled by varying the reaction temperature and silane. A “cesium effect” on both reactions was observed by comparing the catalytic activity of various alkali-metal carbonates. Combined experimental and computational studies suggested the following reaction mechanism: (i) activation of Si?H by Cs2CO3, (ii) insertion of CO2 into Si?H, (iii) formylation of amines by silyl formate, and (iv) reduction of formamides to methylamines.
N-heterocyclic carbene copper(i) catalysed N-methylation of amines using CO2
Santoro, Orlando,Lazreg, Fama,Minenkov, Yury,Cavallo, Luigi,Cazin, Catherine S. J.
, p. 18138 - 18144 (2015/10/28)
The N-methylation of amines using CO2 and PhSiH3 as source of CH3 was efficiently performed using a N-heterocyclic carbene copper(i) complex. The methodology was found compatible with aromatic and aliphatic primary and secondary amines. Synthetic and computational studies have been carried out to support the proposed reaction mechanism for this transformation.
Light-promoted N,N-dimethylation of amine and nitro compound with methanol catalyzed by Pd/TiO2 at room temperature
Zhang, Lina,Zhang, Yan,Deng, Youquan,Shi, Feng
, p. 14514 - 14521 (2015/03/05)
A series of TiO2 supported nano-Pd catalysts (Pd/TiO2) were prepared and used for the N,N-dimethylation of different amines and nitro compounds with methanol under UV irradiation at room temperature. A wide range of N,N-dimethyl amines were one-pot synthesized with up to 98% by applying aliphatic secondary amines, aromatic primary amines, aliphatic primary amines and aromatic nitro compounds as starting materials. It is noteworthy that up to 90% yield of 4-chloro-N,N-dimethylaniline was obtained by adjusting the Pd loadings on the TiO2 and the dehalogenation reaction was inhibited. Finally, a reaction mechanism is discussed, involving PhN = CH2 and PhNHCH3 as reaction intermediates.
Selective methylation of amines with carbon dioxide and H2
Li, Yuehui,Sorribes, Ivan,Yan, Tao,Junge, Kathrin,Beller, Matthias
supporting information, p. 12156 - 12160 (2013/12/04)
Put a label on it: Carbon dioxide with H2 is shown to be an efficient and selective methylation reagent for aromatic and aliphatic amines (see scheme; acac=acetylacetonate, triphos = 1,1,1- tris(diphenylphosphanylmethyl)ethane). A variety of functionalized amines including 13C-labelled drugs were obtained with good yields and functional-group tolerance. Copyright
New deoxygenation method for amine n-oxides using dimethylthiocarbamoyl chloride
Caliskan, Hafize,Zaim, Oemer
experimental part, p. 3078 - 3083 (2010/11/04)
A facile and efficient deoxygenation method for various amine N-oxides to their corresponding amines is described. The experimental procedure is quite simple and the products are obtained in excellent yields. Copyright Taylor & Francis Group, LLC.
Selective N,N-dimethylation of primary aromatic amines with methyl alkyl carbonates in the presence of phosphonium salts
Selva, Maurizio,Perosa, Alvise,Tundo, Pietro,Brunelli, Davide
, p. 5770 - 5773 (2007/10/03)
In the presence of onium salts, at 140-170 °C. methyl alkyl carbonates [1a-c, ROCO2Me, R = MeO(CH2)2[O(CH 2)2]n; n = 2-0, respectively] react with primary aromatic amines (XC6H4NH2, X = p-OMe, p-Me, H, p-Cl, p-CO2Me, o-Et, and 2,3-Me2C 6H3NH2) to yield the corresponding N,N-dimethyl derivatives (ArNMe2) with high selectivity (up to 96%) and good isolated yields (78-95%). Phosphonium salts (e.g., Ph3PEtI and n-Bu4PBr) are particularly efficient catalysts. Overall, a solvent-free reaction is coupled with safe methylating agents (1a-c) made from nontoxic dimethyl carbonate.
