武汉大学雷爱文团队在研究中取得进展。他们的研究实现了氧化羰基化过程中胺的同步识别以合成不对称脲。2024年11月15日出版的《科学》杂志发表了这项成果。

据介绍，不对称脲常见于药品和生物活性化合物中。然而，设计策略来选择性地引入两种不同的胺，来构建不对称脲仍然是一个挑战。

在这项工作中，课题组人员提出了一种同步识别策略，该策略利用自由基和亲核激活来区分仲胺和伯胺。

具体而言，铜催化剂优先将仲胺氧化为自由基，而钴催化剂将伯胺羰基化以产生钴酰胺。这些片段通过协同催化偶联产生具有高选择性的不对称脲，41种生物活性化合物和6种药物的修饰证明了这一点。

附：英文原文

Title: Synchronous recognition of amines in oxidative carbonylation toward unsymmetrical ureas

Author: Jinhui Wang, Shengchun Wang, Zhihong Wei, Pengjie Wang, Yanwei Cao, Yang Huang, Lin He, Aiwen Lei

Issue&Volume: 2024-11-15

Abstract: Unsymmetrical ureas are commonly found in pharmaceuticals and bioactive compounds. However, devising strategies to introduce two distinct amines selectively in the construction of unsymmetrical ureas remains a challenge. In this work, we use a synchronous recognition strategy that takes advantage of radical and nucleophilic activation to discriminate between secondary and primary amines. Specifically, a copper catalyst preferentially oxidizes secondary amines to radical species, whereas a cobalt catalyst carbonylates primary amines to produce cobalt amides. Coupling these fragments by cooperative catalysis produces unsymmetrical ureas with high selectivity, as showcased by the modification of 41 biologically active compounds and six drugs.

DOI: adl0149

Source: https://www.science.org/doi/10.1126/science.adl0149