非均相钴催化剂合成一般功能氨基酸的还原中断串联反应，这一成果由华南理工大学化学与化工学院张敏团队经过不懈努力而取得。2025年2月11日出版的《美国化学会杂志》发表了这项成果。

尽管它们在许多领域具有重要意义，但γ-氨基-α-羟基丁酸（AHBAs）的直接和多样化合成挑战对其功能的探索构成了实质性障碍。通过制备n掺杂碳负载双功能钴催化剂（co - dapen /C），以廉价丰富的硝基芳烃、甲醛和丙烯酸酯为原料，进行串联还原反应，合成AHBA衍生物。这种催化三组分反应具有广泛的底物和功能耐受性，易于获得和可再生的催化剂，以及高台阶和原子经济性。催化剂的活性Co位点参与了甲酸的温和还原过程，而n掺杂碳载体通过物理吸附富集了HCHO和丙烯酸酯，它们分别有利于通过缩合和1,3-偶极环加成捕获羟胺和硝酮中间体。这种金属支撑的协同作用中断了传统的硝基芳烃还原成苯胺的过程，并产生了一种新的串联反应途径。通过合理的催化剂设计，期望将温和还原和有效中间转化相结合的概念能够发展出更有主题的串联反应。

附：英文原文

Title: Reduction-Interrupted Tandem Reaction for General Synthesis of Functional Amino Acids by a Heterogeneous Cobalt Catalyst

Author: Haotian Hua, Chenggang Ci, Pierre H. Dixneuf, Min Zhang

Issue&Volume: February 11, 2025

Abstract: Despite their significant importance in numerous fields, the challenges in direct and diverse synthesis of γ-amino-α-hydroxybutyric acids (AHBAs) pose substantial obstacles to explore their functions. Here, by preparation of a N-doped carbon-supported bifunctional cobalt catalyst (Co-DAPhen/C), it was applied to develop a reductive tandem reaction for general synthesis of AHBA derivatives from cheap and abundant nitroarenes, formaldehyde, and acrylates. This catalytic three-component reaction features broad substrate and functionality tolerance, an easily accessible and reusable catalyst, and high step and atom economy. The active Co sites of the catalyst are involved in the mild reduction processes with formic acid, whereas the N-doped carbon support enriches the HCHO and acrylates by physical adsorption, thus favoring the capture of hydroxylamine and nitrone intermediates via condensation and 1,3-dipolar cycloaddition, respectively. Such a metal–support synergy interrupts the conventional reduction of nitroarenes into anilines and results in a novel tandem reaction route. In this work, the concept merging mild reduction and effective intermediate transformations is anticipated to develop more useful tandem reactions by rational catalyst design.

DOI: 10.1021/jacs.4c15284

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c15284