- Buchwald-Hartwig Amination of Coordinating Heterocycles Enabled by Large-but-Flexible Pd-BIAN-NHC Catalysts**
-
A new class of large-but-flexible Pd-BIAN-NHC catalysts (BIAN=acenaphthoimidazolylidene, NHC=N-heterocyclic carbene) has been rationally designed to enable the challenging Buchwald-Hartwig amination of coordinating heterocycles. This robust class of BIAN-NHC catalysts permits cross-coupling under practical aerobic conditions of a variety of heterocycles with aryl, alkyl, and heteroarylamines, including historically challenging oxazoles and thiazoles as well as electron-deficient heterocycles containing multiple heteroatoms with BIAN-INon (N,N′-bis(2,6-di(4-heptyl)phenyl)-7H-acenaphtho[1,2-d]imidazol-8-ylidene) as the most effective ligand. Studies on the ligand structure and electronic properties of the carbene center are reported. The study should facilitate the discovery of even more active catalyst systems based on the unique BIAN-NHC scaffold.
- Li, Dong-Hui,Lan, Xiao-Bing,Song, A-Xiang,Rahman, Md. Mahbubur,Xu, Chang,Huang, Fei-Dong,Szostak, Roman,Szostak, Michal,Liu, Feng-Shou
-
supporting information
(2021/12/06)
-
- Copper- and Cobalt-Catalyzed Syntheses of Thiophene-Based Tertiary Amines
-
Thienylzinc halides and related compounds prepared by deprotonation followed by transmetalation were used in copper-catalyzed amination using N-benzoyloxy secondary amines. By extending the reaction to 1,5-naphthyridine, it was showed that the competitive dimer formation observed in the case of thiophenes was linked with the low stability of some thienylamines rather than homocoupling. Interestingly, thienylzinc halides and related compounds prepared by transmetalation of thienylmagnesium halides, either prepared from their bromo-precursors or generated by deprotometalation, were satisfactorily employed in cobalt-catalyzed aminations. Finally, aminothiophenes were involved in copper-catalyzed mono- and di-N-arylations, affording differently substituted di- and triphenylamines.
- Bouarfa, Salima,Gra?l, Simon,Ivanova, Maria,Langlais, Timothy,Bentabed-Ababsa, Ghenia,Lassagne, Frédéric,Erb, William,Roisnel, Thierry,Dorcet, Vincent,Knochel, Paul,Mongin, Florence
-
p. 3244 - 3258
(2019/06/08)
-
- A Heteroarylamine Library: Indium-Catalyzed Nucleophilic Aromatic Substitution of Alkoxyheteroarenes with Amines
-
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.).
- Yonekura, Kyohei,Yoshimura, Yasuhiro,Akehi, Mizuri,Tsuchimoto, Teruhisa
-
p. 1159 - 1181
(2018/02/06)
-
- Buchwald-Hartwig amination reaction of aryl halides using heterogeneous catalyst based on Pd nanoparticles decorated on chitosan functionalized graphene oxide
-
In this work, graphene oxide was functionalized with chitosan (GO-Chit) followed by a simple approach for immobilization of palladium nanoparticles onto a chitosan grafted graphene oxide surface. The Pd-nanocomposite (GO-Chit-Pd) was characterized using Transmission Electron Microscopy (TEM), Fourier transforms infrared spectroscopy (FT-IR), and X-ray diffraction (XRD) measurements. The catalytic activity of the prepared heterogeneous graphene oxide functionalized chitosan-palladium (GO-Chit-Pd) was investigated in term of C-N coupling reaction (Buchwald-Hartwig amination reaction of aryl halides) yielding products of N-arylamines. The easy purification, convenient operation, and environmental friendliness, combined with a high yield, render this method viable for use in both laboratory research and larger industrial scales. Studying the reusability of the catalyst in this work showed that it could be reused for five times without obvious loss in catalytic activity.
- Sarvestani, Mosayeb,Azadi, Roya
-
-
- METHOD OF PRODUCING HETEROARYL COMPOUND
-
PROBLEM TO BE SOLVED: To provide a method of producing, with a novel reaction, a heteroaryl compound having a structure in which a heteroatom-containing group is coupled to a heteroaromatic ring skeleton. SOLUTION: The heteroaryl compound production metho
- -
-
Paragraph 0116; 0118
(2016/11/24)
-
- Copper-Catalyzed Electrophilic Amination of Organoaluminum Nucleophiles with O -Benzoyl Hydroxylamines
-
A copper-catalyzed electrophilic amination of aryl and heteroaryl aluminums with N,N-dialkyl-O-benzoyl hydroxylamines that affords the corresponding anilines in good yields has been developed. The catalytic reaction proceeds very smoothly under mild conditions and exhibits good substrate scope. Moreover, the developed catalytic system is also well suited for heteroaryl aluminum nucleophiles, providing facile access to heteroaryl amines.
- Zhou, Shuangliu,Yang, Zhiyong,Chen, Xu,Li, Yimei,Zhang, Lijun,Fang, Hong,Wang, Wei,Zhu, Xiancui,Wang, Shaowu
-
p. 6323 - 6328
(2015/06/30)
-
- Ligand-free C-C and C-N cross-couplings with Pd/Nf-G nanocomposite
-
Abstract The catalytic activity of electrochemical deposited Pd nanoparticles on nafion-graphene support was examined for Buchwald-Hartwig amination reaction and Heck coupling reaction. The developed protocol is very efficient and ecofriendly, providing excellent product yield. The Pd/Nf-G catalyst can be used up to four cycles with slight decrease in catalytic activity.
- Shelkar, Radheshyam S.,Shendage, Suresh S.,Nagarkar, Jayashree M.
-
supporting information
p. 4463 - 4467
(2015/06/30)
-
- Synthesis and structural characterization of palladium(II) thiosemicarbazone complex: Application to the Buchwald-Hartwig amination reaction
-
A simple route to synthesize mononuclear palladium(II) thiosemicarbazone complex has been described. Elemental analysis, spectral methods and single crystal X-ray diffraction analysis were used to confirm the composition of the complex. The new complex acts as an active homogeneous catalyst for the Buchwald-Hartwig amination reaction of a wide range of aryl and heteroaryl halides (bromides and chlorides), including activating, neutral and deactivating substrates, with various secondary amines under optimized conditions.
- Prabhu, Rupesh Narayana,Ramesh, Rengan
-
p. 1120 - 1124
(2013/03/13)
-
- A mild and practical copper catalyzed amination of halothiophenes
-
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.
- Lu, Zhikuan,Twieg, Robert J.
-
p. 903 - 918
(2007/10/03)
-
- A Simple Route to N-Arylated 2-Aminothiophenes as a New Class of Amorphous Glass Forming Molecules
-
(matrix presented) By thermal decarboxylation of N-arylated 2-aminothiophene-5-cacrboxylates, a versatile, heavy-metal free method for preparing the title compounds as new class of highly reactive and easily oxidable, amorphous glass forming molecules has been elaborated.
- Hartmann, Horst,Gerstner, Peter,Rohde, Dirk
-
p. 1673 - 1675
(2007/10/03)
-