西湖大学石航团队开发出苯酚与胺的催化胺化反应。相关研究成果于2022年1月11日发表于国际一流学术期刊《美国化学会杂志》。

鉴于酚类和胺的广泛流行和现成可用性，通过这些起始材料之间的直接偶联合成苯胺将非常有吸引力。

该文中，研究人员描述了铑催化的酚类胺化反应，它提供了以水为唯一副产品的多种苯胺的简明途径。亲砂铑催化剂通过π-配位促进酚类固有的困难酮-烯醇互变异构，能够随后与胺发生脱水缩合。

研究人员通过对大量具有各种电子性质的酚类化合物和各种伯胺和仲胺进行反应，证明了这种氧化还原中性催化的普遍性。包括药物在内的结构复杂生物活性分子的后期功能化的几个例子，进一步说明了该方法的潜在广泛用途。

附：英文原文

Title: Catalytic Amination of Phenols with Amines

Author: Kai Chen, Qi-Kai Kang, Yuntong Li, Wen-Qiang Wu, Hui Zhu, Hang Shi

Issue&Volume: January 11, 2022

Abstract: 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.

DOI: 10.1021/jacs.1c12622

Source: https://pubs.acs.org/doi/10.1021/jacs.1c12622