5405-15-2Relevant articles and documents
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.
Synthesis of an Fe-Pd bimetallic catalyst for: N -alkylation of amines with alcohols via a hydrogen auto-transfer methodology
Wu, Peng-Yu,Lu, Guo-Ping,Cai, Chun
, p. 396 - 404 (2021/01/28)
Hydrogen auto-transfer (HAT) or borrowing hydrogen (BH) methodology which combines dehydrogenation, intermediate reaction and hydrogenation, is recognized as an excellent strategy for one-pot synthesis from an economic and environmental point of view. Although much effort has been made on the development of catalysts for HAT reactions, harsh conditions, external base or large amounts of noble metals are still required in most reported catalysis systems, and thus the exploration of a highly efficient and recyclable heterogeneous catalyst remains meaningful. In this work, a novel bimetallic catalyst, Fe10Pd1/NC500 derived from bimetallic MOF NH2-MIL-101(Fe10Pd1), has been prepared, and the catalyst exhibits superior catalytic performance for the N-alkylation of amines with alcohols via a hydrogen auto-transfer methodology. High yields of the desired products were achieved at 120 °C with an alcohol/amine molar ratio of 2?:?1 and required no external additive or solvent. A distinct enhancement in catalytic performance is observed when compared with monometallic catalysts, which can be ascribed to the "synergistic effects"inside the bimetallic alloys. The N-doped carbon support has been revealed to provide the necessary basicity which avoids the requirement of an external base. Moreover, a wide substrate range and remarkable reusability have been shown by Fe10Pd1/NC500, and this work highlights new possibilities for bimetallic catalysts applied in sustainable chemistry.
Tungsten-Catalyzed Direct N-Alkylation of Anilines with Alcohols
Lan, Xiao-Bing,Ye, Zongren,Yang, Chenhui,Li, Weikang,Liu, Jiahao,Huang, Ming,Liu, Yan,Ke, Zhuofeng
, p. 860 - 865 (2021/01/18)
The implementation of non-noble metals mediated chemistry is a major goal in homogeneous catalysis. Borrowing hydrogen/hydrogen autotransfer (BH/HA) reaction, as a straightforward and sustainable synthetic method, has attracted considerable attention in the development of non-noble metal catalysts. Herein, we report a tungsten-catalyzed N-alkylation reaction of anilines with primary alcohols via BH/HA. This phosphine-free W(phen)(CO)4 (phen=1,10-phenthroline) system was demonstrated as a practical and easily accessible in-situ catalysis for a broad range of amines and alcohols (up to 49 examples, including 16 previously undisclosed products). Notably, this tungsten system can tolerate numerous functional groups, especially the challenging substrates with sterically hindered substituents, or heteroatoms. Mechanistic insights based on experimental and computational studies are also provided.
