128479-57-2Relevant academic research and scientific papers
Catalytic Amination of Phenols with Amines
Chen, Kai,Kang, Qi-Kai,Li, Yuntong,Wu, Wen-Qiang,Zhu, Hui,Shi, Hang
supporting information, p. 1144 - 1151 (2022/02/05)
Given the wide prevalence and ready availability of both phenols and amines, aniline synthesis through direct coupling between these starting materials would be extremely attractive. Herein, we describe a rhodium-catalyzed amination of phenols, which provides concise access to diverse anilines, with water as the sole byproduct. The arenophilic rhodium catalyst facilitates the inherently difficult keto–enol tautomerization of phenols by means of π-coordination, allowing for the subsequent dehydrative condensation with amines. We demonstrate the generality of this redox-neutral catalysis by carrying out reactions of a large array of phenols with various electronic properties and a wide variety of primary and secondary amines. Several examples of late-stage functionalization of structurally complex bioactive molecules, including pharmaceuticals, further illustrate the potential broad utility of the method.
A versatile method for the N,N-dialkylation of aromatic amines via Grignard reactions on N,N-bis(benzotriazolylmethyl)arylamines
Katritzky, Alan R.,Rachwal, Stanislaw,Wu, Jing
, p. 456 - 463 (2007/10/02)
Grignard reactions of N,N-bis(benzotriazolylmethyl)arylamines afford the corresponding N,N-dialkylarylamines in high yields.Electron-releasing substituents on the aryl ring facilitate the reaction.Arylamines are N,N-dialkylated with two different alkyl groups by a stepwise procedure: N-benzotriazolylmethylation of an amine followed by a Grignard reaction to introduce the first alkyl group, and repetition of the same procedure to introduce the second alkyl group.Grignard reagents derived from 1,4-dihalobutane, upon reaction with N,N-bis(benzotriazolylmethyl)arylamines, give the corresponding N-aryl-hexahydroazepines together with acyclic products.
