62121-57-7Relevant academic research and scientific papers
Electrochemical Reductive Arylation of Nitroarenes with Arylboronic Acids
Wang, Dan,Wan, Zhaohua,Zhang, Heng,Alhumade, Hesham,Yi, Hong,Lei, Aiwen
, p. 5399 - 5404 (2021/10/20)
The synthesis of diarylamine is extremely important in organic chemistry. Herein, a novel electrochemical reductive arylation of nitroarenes with arylboronic acids was developed. A variety of diarylamines were synthesized without the need for transition-metal catalysts. The reaction could be scaled up efficiently in a flow cell and several derivatization reactions were carried out smoothly. Cyclic voltammetry experiments and mechanism studies showed that acetonitrile, formic acid, and triethyl phosphite all played a role in promoting this reductive arylation transformation.
Cu(I)–N-heterocyclic carbene-catalyzed base free C–N bond formation of arylboronic acids with amines and azoles
Zhang, Maoyuan,Xu, Zengbing,Shi, Dabin
, (2020/12/25)
A new N-heterocyclic carbene (NHC) precursor of imidazolium chloride and its corresponding Cu(I)–NHC complex 1 was synthesized. The complex 1 was found to be a highly effective catalyst for Chan-Evans-Lam coupling of arylboronic acid with amines and azoles (including imidazole, pyrazole and triazole), without addition of base at room temperature. Various substituents on three substrates can be tolerated, giving the desired coupling products in good to excellent yields (62–94%). The method is practical and offers an alternative to the corresponding copper-catalyzed Chan-Evans-Lam process for the construction of C–N bonds.
Cu-ACP-Am-Fe3O4@SiO2: an efficient and recyclable heterogeneous catalyst for the Chan–Lam coupling reaction of boronic acids and amines
Vibhute, Sandip P.,Mhaldar, Pradeep M.,Gaikwad, Dipak S.,Shejwal, Rajendra V.,Pore, Dattaprasad M.
, p. 87 - 92 (2020/01/03)
Abstract: We have developed an efficient method for Cu-ACP-Am-Fe3O4@SiO2 catalyzed Chan–Lam coupling of phenylboronic acid with primary amine furnished secondary amines. The catalyst offered virtues like mild reaction conditions, magnetically separable, and reusable and exhibits excellent performance in terms of good product yield and high turnover number. Graphic abstract: [Figure not available: see fulltext.]
Activator-Promoted Aryl Halide-Dependent Chemoselective Buchwald-Hartwig and Suzuki-Miyaura Type Cross-Coupling Reactions
Dhital, Raghu N.,Hashizume, Daisuke,Hu, Hao,Ishii, Rikako,Sato, Takuma,Sen, Abhijit,Takaya, Hikaru,Uozumi, Yasuhiro,Yamada, Yoichi M. A.
supporting information, (2020/06/29)
Herein, we report the development of aryl halide-dependent chemoselective reactions, viz., the Buchwald-Hartwig type coupling reaction of an aryl iodide with an arylboronic acid and an aryl amine in the presence of a heterogeneous and reusable nickel catalyst and the Suzuki-Miyaura type coupling of an aryl chloride under similar conditions. Control experiments revealed that the presence of stoichiometric amounts of the phenylboronic acid/ester and aryl amine are essential for both reactions. NMR and XAFS studies suggested the formation of a boron-amine "ate"complex.
PREPARATION OF SECONDARY AMINES WITH ELECTROPHILIC N-LINCHPIN REAGENTS
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Page/Page column 101-102, (2018/12/13)
In one aspect, the present disclosure provides methods of preparing a secondary amine. In some embodiments, the secondary amine comprises two different groups or two identifical groups. Also provided herein are compositions for use in the preparation of the secondary amine.
Copper immobilized at a covalent organic framework: An efficient and recyclable heterogeneous catalyst for the Chan-Lam coupling reaction of aryl boronic acids and amines
Han, Yi,Zhang, Mo,Zhang, Ya-Qing,Zhang, Zhan-Hui
, p. 4891 - 4900 (2018/11/21)
A polyimide covalent organic framework (PI-COF) with high thermal and chemical stabilities has been readily prepared from commercially available and inexpensive reagents and was employed as an effective support for heterogeneous copper. It was demonstrated that the obtained Cu@PI-COF is a highly active heterogeneous catalyst which can effectively promote the Chan-Lam coupling reaction of aryl boronic acids and amines in an open flask without the aid of any base or additive. In addition, the catalyst could be readily recovered from the reaction mixture by simple filtration and reused for at least eight cycles without any observable change in structure and catalytic activity.
Palladium-catalyzed amination of aryl sulfoxides
Yoshida, Yuto,Otsuka, Shinya,Nogi, Keisuke,Yorimitsu, Hideki
supporting information, p. 1134 - 1137 (2018/02/23)
Amination of diaryl sulfoxides with anilines and alkylamines has been accomplished under palladium/N-heterocyclic carbene (NHC) catalysis. Owing to its electron deficiency, the leaving arenesulfenate anion would be smoothly released from the palladium center to result in uneventful catalyst turnover under milder reaction conditions in comparison with previous C-S bond amination reactions. This amination accommodated a wider range of functional groups such as silyl, boryl, methylsulfanyl, and halogen moieties. Regioselective amination of unsymmetrical diaryl sulfoxides was also executed by means of steric bias.
N/O-doped carbon as a "solid ligand" for nano-Pd catalyzed biphenyl- and triphenylamine syntheses
Pang, Shaofeng,Zhang, Yujing,Huang, Yongji,Yuan, Hangkong,Shi, Feng
, p. 2170 - 2182 (2017/07/24)
A series of N/O-doped porous carbon supported nanopalladium catalysts have been successfully prepared, in which the N/O doped carbons were controllably produced via polypyrrole/furan synthesis followed by carbonization. These catalysts exhibit good performance in biphenylamine and triphenylamine syntheses with nitrobenzene and cyclohexanone as starting materials. Their catalytic activity can be tuned efficiently by the N/O functional groups on the carbon surface. TEM, XRD, XPS and laser Raman methods were applied to probe the structure of these catalysts. These results indicate that the Pd nanoparticles were supported on N/O-doped porous carbon via the "coordination" between Pd nanoparticles and N/O functional groups including O-CO, CN and tertiary nitrogen, and better catalytic performance was obtained if carbon with the highest N-species loading was used as the support. In addition, a mechanistic study proved that the reaction starts with the catalytic reduction of nitrobenzene with cyclohexanone as the hydrogen source. During this reaction, aniline was formed and the cyclohexanone was transformed into phenol. Then biphenylamine and triphenylamine were generated through the reaction of aniline and cyclohexanone. This work should facilitate the controllable preparation of carbon supported nanocatalysts with specific activity, and open up a promising pathway for the development of new methodologies for N-containing fine chemical synthesis.
Practical Singly and Doubly Electrophilic Aminating Agents: A New, More Sustainable Platform for Carbon-Nitrogen Bond Formation
Kattamuri, Padmanabha V.,Yin, Jun,Siriwongsup, Surached,Kwon, Doo-Hyun,Ess, Daniel H.,Li, Qun,Li, Guigen,Yousufuddin, Muhammed,Richardson, Paul F.,Sutton, Scott C.,Kürti, László
supporting information, p. 11184 - 11196 (2017/08/21)
Given the importance of amines in a large number of biologically active natural products, active pharmaceutical ingredients, agrochemicals, and functional materials, the development of efficient C-N bond-forming methods with wide substrate scope continues to be at the frontier of research in synthetic organic chemistry. Here, we present a general and fundamentally new synthetic approach for the direct, transition-metal-free preparation of symmetrical and unsymmetrical diaryl-, arylalkyl-, and dialkylamines that relies on the facile single or double addition of readily available C-nucleophiles to the nitrogen atom of bench-stable electrophilic aminating agents. Practical single and double polarity reversal (i.e., umpolung) of the nitrogen atom is achieved using sterically and electronically tunable ketomalonate-derived imines and oximes. Overall, this novel approach represents an operationally simple, scalable, and environmentally friendly alternative to transition-metal-catalyzed C-N cross-coupling methods that are currently used to access structurally diverse secondary amines.
Palladium-catalyzed amination of aryl sulfides with anilines
Sugahara, Tomohiro,Murakami, Kei,Yorimitsu, Hideki,Osuka, Atsuhiro
supporting information, p. 9329 - 9333,5 (2014/11/07)
A combination of a palladium-NHC catalyst and potassium hexamethyldisilazide enables the amination of aryl sulfides with anilines to afford a wide variety of diarylamines. The reaction conditions are versatile enough for the reaction of even bulky ortho-substituted aryl sulfides. This amination can be applied to the modular synthesis of N-aryl carbazoles from the corresponding ortho-bromothioanisoles. As aryl sulfoxides undergo extended Pummerer reactions to afford ortho-substituted aryl sulfides, the Pummerer products are thus useful substrates for the amination to culminate in efficient syntheses of a 2-anilinobenzothiophene and an indole as proof-of-principle of the utility of the extended Pummerer reaction/amination cascade. Switching S to N: Transformation of inert C-S bonds of aryl sulfides into C-N bonds is achieved using a palladium complex with an N-heterocyclic carbene ligand. Thanks to the efficient conditions for amination of bulky sulfides, the synthesis of carbazole products from 2-biphenylylamine is achieved through oxidative C-N bond formation. When combined with extended Pummerer reactions, intriguing nitrogen-containing molecules are prepared.
