1006-76-4Relevant articles and documents
A mild and practical copper catalyzed amination of halothiophenes
Lu, Zhikuan,Twieg, Robert J.
, p. 903 - 918 (2005)
We have found that N,N-dimethylethanolamine (deanol) is a useful solvent and ligand for copper catalyzed amination of a variety of unactivated and activated 2- or 3-halothiophenes. Primary amines, acyclic secondary amines, cyclic secondary amines and acyclic secondary amines with 2-hydroxyethyl functionality react with halothiophenes in moderate to excellent yields. The mildly basic conditions utilized are compatible with many functional groups. The amination of halobithiophenes has also been examined. The aminothiophenes produced by this method are important intermediates in a variety of electronic and optoelectronic materials. We have found that N,N-dimethylethanolamine (deanol) is a useful solvent and ligand for copper catalyzed amination of a variety of unactivated and activated 2- or 3-halothiophenes. Primary amines, acyclic secondary amines, cyclic secondary amines and acyclic secondary amines with 2-hydroxyethyl functionality react with halothiophenes providing the corresponding aminated thiophenes in moderate to excellent yields. The mildly basic conditions utilized are compatible with many functional groups. The amination of halobithiophenes has also been examined. The aminothiophenes produced by this method are important intermediates in a variety of electronic and optoelectronic materials.
Amination of Aryl Halides Mediated by Electrogenerated Nickel from Sacrificial Anode
Daili, Farah,Sengmany, Stéphane,Léonel, Eric
, p. 2462 - 2469 (2021)
Electrochemical C(sp2)?N couplings mediated by nickel salts generated from the sacrificial anode has been described for the first time. In this approach, the sacrificial nickel anode is employed as the sole source of nickel and the process, operationally simple to set up, enables the preparation of functionalized arylamine derivatives with moderate to good yields, under mild reaction conditions and without additional ligand. A cooperative process between the two electrodes is involved in the proposed mechanism.
Skeleton decoration of NHCs by amino groups and its sequential booster effect on the palladium-catalyzed Buchwald-Hartwig amination
Zhang, Yin,Cesar, Vincent,Storch, Golo,Lugan, Noel,Lavigne, Guy
, p. 6482 - 6486 (2014)
A challenging synthetic modification of PEPPSI-type palladium pre-catalysts consisting of a stepwise incorporation of one and two amino groups onto the NHC skeleton was seen to exert a sequential enhancement of the electronic donor properties. This appears to be positively correlated with the catalytic performances of the corresponding complexes in the Buchwald-Hartwig amination. This is illustrated, for example, by the quantitative amination of 4-chloroanisole by morpholine within 2 h at 25°C with a 2 mol% catalyst/substrate ratio or by a significant reduction of catalytic loading (down to 0.005 mol%) for the coupling of aryl chlorides with anilines (max TON: 19600).
An Effective Heterogeneous Copper Catalyst System for C-N Coupling and Its Application in the Preparation of 2-Methyl-4-methoxydiphenylamine (MMDPA)
Yi, Zhou,Huang, Manna,Wan, Yiqian,Zhu, Xinhai
, p. 3911 - 3920 (2018/09/29)
A ligand-recyclable, environmentally benign heterogeneous catalyst system composed of CuI and polystyrene-supported N (-(4-(aminomethyl)naphthalen-1-yl)- N (-phenyl-1 H -pyrrole-2-carbohydrazide (PSAP) has been established for Ullmann type C-N coupling based on the homogeneous catalyst system N ′, N ′-diphenyl-1 H -pyrrole-2-carbohydrazide/CuI. This heterogeneous catalyst system maintained the catalytic effectiveness of the homogeneous catalyst. A variety of functionalized aryl bromides can be efficiently aminated with aryl amines and aliphatic amines with high selectivity for amines over alcohols. Moreover, a practical application of this catalyst system to promote the reaction of commercially available 4-methoxy-2-methylaniline and bromobenzene in 10 mmol scale, provided 2-methyl-4-methoxydiphenylamine (MMDPA) with 93% yield with the merit of the approach being simple operation for work-up and purification.
A Heteroarylamine Library: Indium-Catalyzed Nucleophilic Aromatic Substitution of Alkoxyheteroarenes with Amines
Yonekura, Kyohei,Yoshimura, Yasuhiro,Akehi, Mizuri,Tsuchimoto, Teruhisa
, p. 1159 - 1181 (2018/02/06)
Under indium Lewis acid catalysis, electron-rich five-membered heteroaryl electrophiles fused with/without a benzene ring were found to couple with amines to produce heteroarylamines with broad structural diversity. The heteroarylamine formation proceeds through the cleavage of a heteroaryl?OMe bond by the nucleophilic attack of the amine based on the nucleophilic aromatic substitution (SNAr) reaction. In contrast to the corresponding traditional SNAr amination, the present SNAr-based heteroaryl amination can be performed without relying on both heteroaryl electrophiles with electron-withdrawing groups and nucleophilicity-enhanced metal amides. High compatibility towards the functional groups such as NO2, Br, I, CF3, CN, CO2Et, pyridyl, thiazolyl, C=C, and OH groups was observed, thus showing the practicality and reliability of this method. Mechanistic studies indicated that a carbon?indium bond is likely to be formed on the heteroaryl ring during the process. (Figure presented.).
