- Highly Efficient Binuclear Copper-catalyzed Oxidation of N,N-Dimethylanilines with O2
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A binuclear copper-salicylate complex, [Cu(Sal)2(NCMe)]2 (Sal=salicylate), was found to be an active catalyst for the oxidation of N,N-dimethylanilines by O2, affording the corresponding N-methyl-N-phenylformamides as major products. The reactions were carried out with a O2 balloon and the S/C (substrate/catalyst ratio) of the model reaction could be up to 1×105, providing a practical and highly efficient catalytic protocol for accessing N-methyl-N-phenylformamides.
- Liu, Yuxia,Yan, Yonggang,Xue, Dong,Wang, Zhongfu,Xiao, Jianliang,Wang, Chao
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p. 2221 - 2225
(2020/03/23)
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- An efficient method for the N-formylation of amines under catalyst- and additive-free conditions
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A simple catalyst- and additive-free method for the N-formylation of amines has been developed. The advantages of this protocol include a wide range of functional group tolerance, high efficiency and a lack of required extra promoters under mild conditions. This convenient strategy will provide a facile synthesis towards N-formamide natural products and pharmaceutical derivatives. A mechanism that involves difluorocarbene is proposed for this reaction.
- Xu, Zhuo-Wei,Xu, Wen-Yi,Pei, Xiao-Jun,Tang, Fei,Feng, Yi-Si
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supporting information
p. 1254 - 1258
(2019/04/10)
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- N-aryl formamide prepared by using ethyl bromodifluoroacetate as formylating reagent
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The invention discloses a compound of N-aryl formamide prepared by using ethyl bromodifluoroacetate as a formylating reagent. The compound is prepared by using N-alkyl arylamine as a raw material, ethyl bromodifluoroacetate as a formylating reagent and copper as a catalyst, adding different ligands, bases, etc., performing reaction under stirring in a reaction solvent at 100-120 DEG C for 10-14 hours; then filtering the reaction solution to obtain filtrate after reaction ending; concentrating the filtrate, removing the solvent by using a rotary evaporator to obtain a residue, treating the residue by silica gel column chromatography, eluting with an eluent, collecting the effluent according to the actual gradient; combining the effluent containing the product, concentrating the combined effluent to remove the solvent, and performing vacuum drying to obtain the target product. The compound has the advantages of simple and easily obtained raw materials, simple preparation process, less pollution, low energy consumption and high yield.
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Paragraph 0033
(2018/12/02)
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- Copper-Catalyzed N-Formylation of Amines through Tandem Amination/Hydrolysis/Decarboxylation Reaction of Ethyl Bromodifluoroacetate
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Ethyl bromodifluoroacetate (BrCF2COOEt) was first used as the N-formylating reagent in the copper-catalyzed N-formylation of amines. A range of primary, secondary, cyclic arylamines, and aliphatic amines underwent the N-formylation smoothly to furnish the N-formamides in moderate-to-excellent yields.
- Li, Xiao-Fang,Zhang, Xing-Guo,Chen, Fan,Zhang, Xiao-Hong
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p. 12815 - 12821
(2018/10/20)
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- Electrochemical N -Formylation of Amines via Decarboxylation of Glyoxylic Acid
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A new method for the synthesis of formamides has been developed through electrochemical decarboxylative N-formylation of amines with glyoxylic acid. This protocol provides an efficient approach to formamides with a broad range of functional group tolerance under ambient conditions.
- Lin, Dian-Zhao,Huang, Jing-Mei
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supporting information
p. 2112 - 2115
(2018/04/14)
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- Visible-light-induced oxidative formylation of N-alkyl-N-(prop-2-yn-1-yl)anilines with molecular oxygen in the absence of an external photosensitizer
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Visible-light-induced oxidative formylation of N-alkyl-N-(prop-2-yn-1-yl)anilines with molecular oxygen in the absence of an external photosensitizer was developed and afforded the corresponding formamides in good yields under mild conditions. The investigation of the mechanism disclosed that both the starting material and the product act as photosensitizers, and 1O2 and O2- are generated through energy transfer and a single electron transfer pathway and play an important role in the reaction.
- Ji, Wangqin,Li, Pinhua,Yang, Shuai,Wang, Lei
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supporting information
p. 8482 - 8485
(2017/08/03)
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- Photoinduced Oxidative Formylation of N,N-Dimethylanilines with Molecular Oxygen without External Photocatalyst
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A photoinduced oxidative formylation of N,N-dimethylanilines with molecular oxygen in the absence of an external photocatalyst was developed and provided the corresponding formamides in good yields under mild reaction conditions. Investigations indicated that both the starting material and product act as photosensitizers and that 1O2 coexists with O2?- during the reaction through energy transfer and single electron transfer process.
- Yang, Shuai,Li, Pinhua,Wang, Zhihui,Wang, Lei
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supporting information
p. 3386 - 3389
(2017/07/15)
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- Selective formylation and methylation of amines using carbon dioxide and hydrosilane catalyzed by alkali-Metal carbonates
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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.
- Fang, Chi,Lu, Chunlei,Liu, Muhua,Zhu, Yiling,Fu, Yao,Lin, Bo-Lin
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p. 7876 - 7881
(2018/05/23)
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- Fluoro-functionalized polymeric N-heterocyclic carbene-zinc complexes: Efficient catalyst for formylation and methylation of amines with CO2 as a C1-building block
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A fluoro-functionalized polymeric N-heterocyclic carbene (NHC)-Zn complex (F-PNHC-Zn) was designed and synthesized by taking fluorous imidazolium salts as precursors through a two-step alkylation. The resultant F-PNHC-Zn was applied in catalyzing the formylation and methylation of amines using CO2 as a C1 building block in the presence of organosilane, which showed much higher activity than the corresponding non-fluorous PNHC-Zn under identical conditions. N-Methylanilines with both electron-withdrawing and electron-donating groups all could be converted to the corresponding formamides and methylamines in >90% conversion. Quantitative conversion of N-methylaniline was obtained even under very low CO2 pressure (0.05 MPa diluted by N2). Moreover, F-PNHC-Zn was highly stable and easily recyclable for these reactions. This journal is
- Yang, Zhen-Zhen,Yu, Bo,Zhang, Hongye,Zhao, Yanfei,Ji, Guipeng,Liu, Zhimin
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p. 19613 - 19619
(2015/06/09)
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- CO2 as a C1-building block for the catalytic methylation of amines
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A novel catalytic reaction has been designed to utilize, for the first time, CO2 as a C1 feedstock in the synthesis of N-methylamines. Simple zinc catalysts, based on commercially available zinc salts and ligands, prove highly efficient in promoting both a 6 electron reduction of carbon dioxide and the formation of a C-N bond, using hydrosilanes and amines.
- Jacquet, Olivier,Frogneux, Xavier,Das Neves Gomes, Christophe,Cantat, Thibault
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p. 2127 - 2131
(2013/05/21)
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- One-Pot Monomethylation of Substituted Anilines by Phase Transfer Catalyst
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A one-pot monomethylation of substituted anilines (1) by phase transfer catalysis has been developed.The primary amino function of 1 is protected by treatment with formic acid to give N-formylanilines (2) which are methylated in situ with dimethyl sulphate in the presence of tetrabutylammonium hydrogen sulphate, anhyd.K2CO3 and powdered NaOH.The resultant N-formyl-N-methylanilines (3) on deformylation by boiling with water furnish N-methyl-anilines (4) in high yields with >95percent purity.
- Sharma, V. K.,Kumar, A.,Agarwal, K. P.
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