3416-49-7Relevant academic research and scientific papers
Dirhodium-Catalyzed Chemo-and Site-Selective C-H Amidation of N, N-Dialkylanilines
Chen, Gong,Arai, Kenta,Morisaki, Kazuhiro,Kawabata, Takeo,Ueda, Yoshihiro
supporting information, p. 728 - 732 (2021/01/18)
A method for dirhodium-catalyzed C(sp 3)-H amidation of N, N-dimethylanilines was developed. Chemoselective C(sp 3)-H amidation of N-methyl group proceeded exclusively in the presence of C(sp 2)-H bonds of the electron-rich aromatic ring. Site-selective C(sp 3)-H amidation proceeded exclusively at the N-methyl group of N-methyl-N-Alkylaniline derivatives with secondary, tertiary, and benzylic C(sp 3)-H bonds α to a nitrogen atom.
Visible-Light-Induced C(sp2)-C(sp3) Cross-Dehydrogenative-Coupling Reaction of N-Heterocycles with N-Alkyl- N-methylanilines under Mild Conditions
Zhang, Hong-Yu,Chen, Jianjun,Lu, Cong-Cong,Han, Ya-Ping,Zhang, Yuecheng,Zhao, Jiquan
, p. 11723 - 11735 (2021/09/02)
Disclosed herein is a cross-dehydrogenative-coupling reaction of N-heterocycles including 1,2,4-triazine-3,5(2H, 4H)-diones and quinoxaline-2(1H)-ones with N-methylanilines to form C(sp2)-C(sp3) under visible-light illumination and ambient air at room temperature. In this process, easily available Ru(bpy)3Cl2·6H2O serves as the catalyst, and air acts as the green oxidant. This method features high atom economy, environmental friendliness, and convenient operation and provides an efficient and practical access to aminomethyl-substituted N-heterocycles with extensive functional group compatibility in 40-86% yields.
Visible light-induced N-methyl activation of unsymmetric tertiary amines
Perumal, Gopi,Kandasamy, Mohanraj,Ganesan, Balaji,Govindan, Karthick,Sathya, Harsha,Hung, Min-Yuan,Chandru Senadi, Gopal,Wu, Ya-Ching,Lin, Wei-Yu
, (2021/01/09)
In the presence of methylene group, selective N-methyl activation of tertiary amines has been accomplished with the aid of visible light using organic photocatalyst under air. This protocol explores numerous aliphatic and aromatic substituted tetra-hydroquinoline analogues from various tertiary amines and maleimides. Furthermore, this approach was applied to activate the methyl group of N-methyl carbazole to generate the biologically active molecule.
Selective: N-formylation/N-methylation of amines and N-formylation of amides and carbamates with carbon dioxide and hydrosilanes: Promotion of the basic counter anions of the zinc catalyst
Zhang, Qiao,Lin, Xiao-Tao,Fukaya, Norihisa,Fujitani, Tadahiro,Sato, Kazuhiko,Choi, Jun-Chul
supporting information, p. 8414 - 8422 (2020/12/29)
A catalyst composed of commercially available Zn(OAc)2 and 1,10-phenanthroline (phen) was effective in the N-formylation/N-methylation of amines using CO2 as the C1 source in the presence of hydrosilanes. An equimolar reaction of N-methylaniline with PhSiH3 under a CO2 atmosphere yielded the N-formylation product in 92% yield at 25 °C. Scale-up of the reaction using 10 mmol substrate was also successful in affording the desired product in 83% yield (1.1 g). This catalyst exhibits a high thermal stability and a turnover number (TON) of 385000 at 150 °C. In addition, the reaction of N-methylaniline in the presence of excess Ph2SiH2 produced N,N-dimethylaniline. Furthermore, our catalytic protocol was developed for the N-formylation of amides and carbamates, which have smaller pKa values and lower reactivities than the corresponding amines. The present Zn(OAc)2/phen catalyst was found to show versatility in the conversion of CO2 and amines into several functionalized organic chemicals under mild conditions. We propose that the basic counter anion (i.e., the acetate) of the catalyst activates both the Si-H and N-H bonds.
Mn-Catalyzed Selective Double and Mono-N-Formylation and N-Methylation of Amines by using CO2
Huang, Zijun,Jiang, Xiaolin,Zhou, Shaofang,Yang, Peiju,Du, Chen-Xia,Li, Yuehui
, p. 3054 - 3059 (2019/04/10)
Functionalization of amines by using CO2 is of fundamental importance considering the abundance of amines and CO2. In this context, the catalytic formylation and methylation of amines represent convenient and successful protocols for selective CO2 utilization as a C1 building block. This study represents the first example of selective catalytic double N-formylation of aryl amines by using a dinuclear Mn complex in the presence of phenylsilane. This robust system also allows for selective formylation and methylation of amines under a range of conditions.
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.
Tailored Cobalt-Catalysts for Reductive Alkylation of Anilines with Carboxylic Acids under Mild Conditions
Liu, Weiping,Sahoo, Basudev,Spannenberg, Anke,Junge, Kathrin,Beller, Matthias
supporting information, p. 11673 - 11677 (2018/09/10)
The first cobalt-catalyzed hydrogenative N-methylation and alkylation of amines with readily available carboxylic acid feedstocks as alkylating agents and H2 as ideal reductant is described. Combination of tailor-made triphos ligands with cobalt(II) tetrafluoroborate significantly improved the efficiency, thus promoting the reaction under milder conditions. This novel protocol allows for a broad substrate scope with good functional group tolerance, even in the presence of reducible alkenes, esters, and amides.
Cu-Catalyzed Cross-Dehydrogenative ortho-Aminomethylation of Phenols
Yu, Congjun,Patureau, Frederic W.
supporting information, p. 11807 - 11811 (2018/09/10)
A highly selective CuII-catalyzed cross-dehydrogenative ortho-aminomethylation of phenols with aniline derivatives is described. The corresponding C(sp2)?C(sp3) coupling products were obtained in moderate to excellent yields under mild reaction conditions and with a broad substrate scope. A radical mechanism is proposed.
Synthesis of Halogenated Anilines by Treatment of N, N-Dialkylaniline N-Oxides with Thionyl Halides
Reed, Hayley,Paul, Tyler R.,Chain, William J.
, p. 11359 - 11368 (2018/08/06)
The special reactivity of N,N-dialkylaniline N-oxides allows practical and convenient access to electron-rich aryl halides. A complementary pair of reaction protocols allow for the selective para-bromination or ortho-chlorination of N,N-dialkylanilines in up to 69% isolated yield. The generation of a diverse array of halogenated anilines is made possible by a temporary oxidation level increase of N,N-dialkylanilines to the corresponding N,N-dialkylaniline N-oxides and the excision of the resultant weak N-O bond via treatment with thionyl bromide or thionyl chloride at low temperature.
Making Copper(0) Nanoparticles in Glycerol: A Straightforward Synthesis for a Multipurpose Catalyst
Dang-Bao, Trung,Pradel, Christian,Favier, Isabelle,Gómez, Montserrat
, p. 2832 - 2846 (2017/08/23)
Small zero-valent copper nanoparticles (CuNPs) have been straightforwardly prepared from Cu(I) and Cu(II) precursors in glycerol and in the presence of polyvinylpyrrolidone as stabilizer. Thanks to the negligible vapor pressure of the solvent, these original nano-systems could be directly characterized in glycerol as well as in the solid state, exhibiting relevantly homogeneous colloidal dispersions, also even after catalysis. CuNPs coming from the well-defined coordination complex di-μ-hydroxobis[(N,N,N′,N′-tetramethylethylenediamine)copper(II)] chloride {[Cu(κ2-N,N-TMEDA)(μ-OH)]2Cl2} have been highly efficient in C–C and C–heteroatom bond formation processes. This new catalytic system has proved its performance in C–N couplings and in the synthesis of differently substituted propargylic amines through cross-dehydrogenative couplings, multi-component reactions such as A3 (aldehyde-alkyne-amine) and KA2 (ketone-alkyne-amine) couplings, as well as in the formation of heterocycles such as benzofurans, indolizines, and quinolines under smooth conditions. No significant copper amount was detected in the extracted organic compounds from the catalytic phase by inductively coupled plasma-atomic emission spectroscopic (ICP-AES) analyses, proving a highly efficient immobilization of copper nanoparticles in glycerol. From a mechanistic point of view, spectroscopic data (infrared and ultraviolet-visible spectra) agree with a surface-like catalytic reactivity. (Figure presented.).
