16350-99-5Relevant academic research and scientific papers
Design of Lewis base functionalized ionic liquids for the N-formylation of amines with CO2 and hydrosilane: The cation effects
Li, Xiao-Ya,Fu, Hong-Chen,Liu, Xiao-Fang,Yang, Shu-Han,Chen, Kai-Hong,He, Liang-Nian
, p. 563 - 569 (2020)
A series of functionalized ionic liquids (ILs) were developed for the reductive functionalization of CO2 with amine and hydrosilane to afford formamides under mild conditions. It was found that 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)-based IL i.e. [DBUC12]Br showed high efficiency for the N-formylation reaction of amines without using any organic solvents or additives. Furthermore, control experiments suggested the cations with active hydrogen may weaken the nucleophilicity of anions through ion pairing interactions, thereby affecting the activation of hydrosilane. The reaction mechanism was then investigated by Density Functional Theory (DFT) calculations. This protocol represents a highly efficient and environmentally friendly example for catalytic conversion of CO2 into value-added chemicals such as formamide derivatives by employing DBU functionalized ILs.
HCl-mediated transamidation of unactivated formamides using aromatic amines in aqueous media
Dhawan, Sanjeev,Girase, Pankaj Sanjay,Kumar, Vishal,Karpoormath, Rajshekhar
, p. 3729 - 3739 (2021/10/14)
We report transamidation protocol to synthesize a range of secondary and tertiary amides from weakly nucleophilic aromatic and hetero-aryl amines with low reactive formamide derivatives, utilizing hydrochloric acid as catalyst. This current acid mediated strategy is beneficial because it eliminates the need for a metal catalyst, promoter or additives in the reaction, simplifies isolation and purification. Notably, this approach conventionally used to synthesize molecules on gram scales with excellent yields and a high tolerance for functional groups.
Tetracoordinate borates as catalysts for reductive formylation of amines with carbon dioxide
Du, Chen-Xia,Huang, Zijun,Jiang, Xiaolin,Li, Yuehui,Makha, Mohamed,Wang, Fang,Zhao, Dongmei
supporting information, p. 5317 - 5324 (2020/09/17)
We report sodium trihydroxyaryl borates as the first robust tetracoordinate organoboron catalysts for reductive functionalization of CO2. These catalysts, easily synthesized from condensing boronic acids with metal hydroxides, activate main group element-hydrogen (E-H) bonds efficiently. In contrast to BX3 type boranes, boronic acids and metal-BAr4 salts, under transition metal-free conditions, sodium trihydroxyaryl borates exhibit high reactivity of reductive N-formylation toward a variety of amines (106 examples), including those with functional groups such as ester, olefin, hydroxyl, cyano, nitro, halogen, MeS-, ether groups, etc. The over-performance to catalyze formylation of challenging pyridyl amines affords a promising alternative method to the use of traditional formylation reagents. Mechanistic investigation supports electrostatic interactions as the key for Si/B-H activation, enabling alkali metal borates as versatile catalysts for hydroborylation, hydrosilylation, and reductive formylation/methylation of CO2.
Ligand-Enabled Ni-Al Bimetallic Catalysis for Nonchelated Dual C-H Annulation of Arylformamides and Alkynes
Luan, Yu-Xin,Wang, Yin-Xia,Ye, Mengchun,Zhang, Feng-Ping
supporting information, (2020/03/19)
A bifunctional secondary phosphine oxide (SPO) ligand-controlled method was developed for Ni-Al-catalyzed nonchelated dual C-H annulation of arylformamides with alkynes, providing a series of substituted amide-containing heterocycles in ≤97% yield. The SPO-bound bimetallic catalysis proved to be critical to the reaction efficiency.
The synthesis of cyanoformamides via a CsF-promoted decyanation/oxidation cascade of 2-dialkylamino-malononitriles
Lei, Lin-Sheng,Xue, Cao-Gen,Xu, Xue-Tao,Jin, Da-Ping,Wang, Shao-Hua,Bao, Wen,Liang, Huan,Zhang, Kun,Asiri, Abdullah M.
supporting information, p. 3723 - 3726 (2019/04/17)
A mild and efficient method for the synthesis of cyanoformamides from N,N-disubstituted aminomalononitriles with CsF as the promoter has been developed. This method features a wide substrate scope and high reaction efficiency, and will facilitate corresponding cyanoformamide-based biological studies and synthetic methodology development.
An efficient method for the N-formylation of amines under catalyst- and additive-free conditions
Xu, Zhuo-Wei,Xu, Wen-Yi,Pei, Xiao-Jun,Tang, Fei,Feng, Yi-Si
supporting information, p. 1254 - 1258 (2019/04/10)
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.
Eco-friendly acetylcholine-carboxylate bio-ionic liquids for controllable: N-methylation and N-formylation using ambient CO2 at low temperatures
Zhao, Wenfeng,Chi, Xiaoping,Li, Hu,He, Jian,Long, Jingxuan,Xu, Yufei,Yang, Song
supporting information, p. 567 - 577 (2019/02/14)
Catalytic fixation of CO2 to produce valuable fine chemicals is of great significance to develop a green and sustainable circulation of excessive carbon in the environment. Herein, a series of non-toxic, biodegradable and recyclable acetylcholine-carboxylate bio-ionic liquids with different cations and anions were simply synthesized for producing formamides and methylamines using atmospheric CO2 as a carbon source, and phenylsilane as a hydrogen donor. The selectivity toward products was tuned by altering the reaction temperature under solvent or solvent-free conditions. N-Methylamines (ca. 96% yield) were obtained in acetonitrile at 50 °C, while N-formamides (ca. 99% yield) were attained without a solvent at 30 °C. The established bio-ionic liquid catalytic system found a wide range of applicability in substrates and possessed a high potentiality in scale-up to gram-grade production. The developed catalytic system was fairly stable, which could be easily reused without an apparent loss of reactivity, possibly due to the strong electrostatic interactions between the cation and anion. The combination of experimental and computational results explicitly elucidated the reaction mechanism: PhSiH3 activated by a bio-IL was favorable for the formation of silyl formate from hydrosilylation of CO2, followed by a reaction with an amine to give an N-formamide, while an N-methylamine was formed by further hydrosilylation of the N-formamide.
Catalyst-Free Transamidation of Aromatic Amines with Formamide Derivatives and Tertiary Amides with Aliphatic Amines
Yin, Jiawen,Zhang, Jingyu,Cai, Changqun,Deng, Guo-Jun,Gong, Hang
supporting information, p. 387 - 392 (2019/01/11)
A simple catalyst- and promoter-free protocol has been developed for the transamidation of weakly nucleophilic aromatic amines with formamide derivatives and low-reactivity tertiary amides with aliphatic amines. This strategy is advantageous because no catalyst or promoters are needed, no additives are required, separation and purification is easy, and the reaction is scalable. Significantly, this strategy was further applied to synthesize several pharmaceutical molecules on a gram scale, and excellent yields were achieved.
N-aryl formamide prepared by using ethyl bromodifluoroacetate as formylating reagent
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Paragraph 0040, (2018/12/02)
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.
Copper-Catalyzed N-Formylation of Amines through Tandem Amination/Hydrolysis/Decarboxylation Reaction of Ethyl Bromodifluoroacetate
Li, Xiao-Fang,Zhang, Xing-Guo,Chen, Fan,Zhang, Xiao-Hong
, p. 12815 - 12821 (2018/10/20)
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.
