14268-66-7Relevant academic research and scientific papers
Regioselective Synthesis of 2-Amino-5-(or 3-)arylazo-Substituted Pyridines and Pyrazines from Pyridinium N-Aminides
Gala, Elena,Reyes, M. José,Alvarez-Builla, Julio,Izquierdo, M. Luisa
, p. 2145 - 2156 (2016)
Differently modified 2-aminopyridines and pyrazines bearing an arylazo group at the 3- or 5-position have been generated from pyridinium N-aminides in a regioselective fashion. The detailed chemistry starts with attack of the N-aminide on a diazonium salt, to form the arylazo derivative. N-alkylation on the exocyclic nitrogen and reduction to break the N-N bond then affords the final compounds, as an extension of the broad synthetic uses of the pyridinium N-aminides.
Chemoselective Hydrogenation of Nitroarenes Using an Air-Stable Base-Metal Catalyst
Zubar, Viktoriia,Dewanji, Abhishek,Rueping, Magnus
supporting information, p. 2742 - 2747 (2021/05/05)
The reduction of nitroarenes to anilines as well as azobenzenes to hydrazobenzenes using a single base-metal catalyst is reported. The hydrogenation reactions are performed with an air-and moisture-stable manganese catalyst and proceed under relatively mild reaction conditions. The transformation tolerates a broad range of functional groups, affording aniline derivatives and hydrazobenzenes in high yields. Mechanistic studies suggest that the reaction proceeds via a bifunctional activation involving metal-ligand cooperative catalysis.
Biorenewable carbon-supported Ru catalyst for: N -alkylation of amines with alcohols and selective hydrogenation of nitroarenes
Goyal, Vishakha,Narani, Anand,Natte, Kishore,Poddar, Mukesh Kumar,Ray, Anjan,Sarki, Naina,Tripathi, Deependra
, p. 14687 - 14694 (2021/08/23)
Herein, we developed a renewable carbon-supported Ru catalyst (Ru/PNC-700), which was facilely prepared via simple impregnation followed by the pyrolysis process. The prepared Ru/PNC-700 catalyst demonstrated remarkable catalytic activity in terms of conversion and selectivity towards N-alkylation of anilines with benzyl alcohol and chemoselective hydrogenation of aromatic nitro compounds. In addition, local anesthetic pharmaceutical agents (e.g., butamben and benzocaine), including key drug intermediates, were synthesized in excellent yields under mild conditions and in the presence of water as a green solvent. Moreover, the prepared Ru/PNC-700 catalyst could be easily recovered and reused up to five times without any apparent loss in activity and selectivity.
Cyclic (Alkyl)(amino)carbene Ligand-Promoted Nitro Deoxygenative Hydroboration with Chromium Catalysis: Scope, Mechanism, and Applications
Zhao, Lixing,Hu, Chenyang,Cong, Xuefeng,Deng, Gongda,Liu, Liu Leo,Luo, Meiming,Zeng, Xiaoming
supporting information, p. 1618 - 1629 (2021/01/25)
Transition metal catalysis that utilizes N-heterocyclic carbenes as noninnocent ligands in promoting transformations has not been well studied. We report here a cyclic (alkyl)(amino)carbene (CAAC) ligand-promoted nitro deoxygenative hydroboration with cost-effective chromium catalysis. Using 1 mol % of CAAC-Cr precatalyst, the addition of HBpin to nitro scaffolds leads to deoxygenation, allowing for the retention of various reducible functionalities and the compatibility of sensitive groups toward hydroboration, thereby providing a mild, chemoselective, and facile strategy to form anilines, as well as heteroaryl and aliphatic amine derivatives, with broad scope and particularly high turnover numbers (up to 1.8 × 106). Mechanistic studies, based on theoretical calculations, indicate that the CAAC ligand plays an important role in promoting polarity reversal of hydride of HBpin; it serves as an H-shuttle to facilitate deoxygenative hydroboration. The preparation of several commercially available pharmaceuticals by means of this strategy highlights its potential application in medicinal chemistry.
Selective Carbon-Carbon Bond Amination with Redox-Active Aminating Reagents: A Direct Approach to Anilines?
Qiu, Xu,Wang, Yachong,Su, Lingyu,Jin, Rui,Song, Song,Qin, Qixue,Li, Junhua,Zong, Baoning,Jiao, Ning
, p. 3011 - 3016 (2021/09/13)
Amines are among the most fundamental motifs in chemical synthesis, and the introduction of amine building blocks via selective C—C bond cleavage allows the construction of nitrogen compounds from simple hydrocarbons through direct skeleton modification. Herein, we report a novel method for the preparation of anilines from alkylarenes via Schmidt-type rearrangement using redox-active amination reagents, which are easily prepared from hydroxylamine. Primary amines and secondary amines were prepared from corresponding alkylarenes or benzyl alcohols under mild conditions. Good compatibility and valuable applications of the transformation were also displayed.
One-Pot Generation of Benzynes from Phenols: Formation of Primary Anilines by the Deoxyamination of Phenols
Akai, Shuji,Ikawa, Takashi,Masuda, Shigeaki
, (2020/03/23)
Benzynes were selectively generated in situ from phenols and trapped regioselectively with potassium hexamethyldisilazide to form primary anilines following acidic workup. The direct conversion of a phenolic hydroxyl group into a free amino group is a useful method for the preparation of primary aryl amines that are hard to synthesize by using coupling reactions involving phenol derivatives with ammonia. Whereas reactions of ortho- and meta-substituted phenols produced meta-substituted anilines exclusively, those of para-substituted phenols provided ortho-silylanilines.
C-H Amination of Arenes with Hydroxylamine
See, Yi Yang,Sanford, Melanie S.
supporting information, p. 2931 - 2934 (2020/04/09)
This Letter describes the development of a TiIII-mediated reaction for the C-H amination of arenes with hydroxylamine. This reaction is applied to a variety of electron-rich (hetero)arene substrates, including a series of natural products and pharmaceuticals. It offers the advantages of mild conditions (room temperature), fast reaction rates (30 min), compatibility with ambient moisture and air, scalability, and the use of inexpensive commercial reagents.
Deacetylative Amination of Acetyl Arenes and Alkanes with C-C Bond Cleavage
Hyodo, Kengo,Hasegawa, Genna,Maki, Hiroya,Uchida, Kingo
supporting information, p. 2818 - 2822 (2019/04/25)
The Br?nsted acid-catalyzed synthesis of primary amines from acetyl arenes and alkanes with C-C bond cleavage is described. Although the conversion from an acetyl group to amine has traditionally required multiple steps, the method described herein, which uses an oxime reagent as an amino group source, achieves the transformation directly via domino transoximation/Beckmann rearrangement/Pinner reaction. The method was also applied to the synthesis of γ-aminobutyric acids, such as baclophen and rolipram.
Oxalic amide ligands, and uses thereof in copper-catalyzed coupling reaction of aryl halides
-
Page/Page column 89-90, (2020/01/09)
The present invention provides oxalic amide ligands and uses thereof in copper-catalyzed coupling reaction of aryl halides. Specifically, the present invention provides a use of a compound represented by formula I, wherein definitions of each group are described in the specification. The compound represented by formula I can be used as a ligand in copper-catalyzed coupling reaction of aryl halides for the formation of C—N, C—O and C—S bonds.
HETEROCYCLIC CARBOXYLIC ACID AMIDE LIGAND AND APPLICATIONS THEREOF IN COPPER CATALYZED COUPLING REACTION OF ARYL HALOGENO SUBSTITUTE
-
Paragraph 0266-0267, (2019/05/15)
Provided are a heterocyclic carboxylic acid amide ligand and applications thereof in a copper catalyzed coupling reaction. Specifically, provided are uses of a compound represented by formula (I), definitions of radical groups being described in the specifications. The compound represented by formula (I) can be used as the ligand in the copper catalyzed coupling reaction of the aryl halogeno substitute, and is used or catalyzing the coupling reaction for forming the aryl halogeno substitute having C—N, C—O, C—S and other bonds.
