南京中医药大学药学院张毅楠课题组取得一项新突破。他们提出了镍钴双金属策略使多芳烃与惰性烷基氯的区域选择性C8–；H烷基化。该研究于2025年2月11日发表于国际一流学术期刊《中国化学》杂志上。

区域选择性C8报道了用惰性氯烷基进行多芳烃H烷基化反应的实例。该反应通过廉价过渡金属镍和钴的协同参与进行。这种方法使各种取代的多芳环与广泛的伯和仲烷基氯化物的偶联成为可能。进一步的合成应用提供了一系列到主题构建块的简单转换，这表明它在复杂分子的后期功能化方面的潜力。机理研究表明，该反应经历了一个自由基过程，非极性Ni（II）→Ni（III）→Ni(I)循环负责决定速率的C氯烷烃与Co(I)的2电子氧化加成均解产生的烷基自由基的H插入。

附：英文原文

Title: Nickel-Cobalt Bimetallic Strategy Enables Regioselective C8–H Alkylation of Polyaromatics with Inert Alkyl Chlorides

Author: Wanbin Song, Ximeng Shi, Wen Li, Shuang Yao, Yujian Mao, Yinan Zhang

Issue&Volume: 2025-02-11

Abstract: A regioselective C8H alkylation of polyaromatics exampled with inert alkyl chloride is reported. The reaction proceeds via the synergistic participation of inexpensive transition metals nickel and cobalt. This approach enables the coupling of various substituted polyaromatic rings with a broad range of primary and secondary alkyl chlorides. Further synthetic applications provide a series of simple conversions to useful building blocks, suggesting its potency in the late-stage functionalization of complex molecules. Mechanistic investigation illustrates that the reaction goes through a radical process with an unusual Ni(II)→Ni(III)→Ni(I) cycle being responsible for the rate-determining CH insertion of alkyl radicals, which are generated by the homolysis of chloroalkane with 2-electrons oxidative addition of Co(I).

DOI: 10.1002/cjoc.202401211

Source: https://onlinelibrary.wiley.com/doi/full/10.1002/cjoc.202401211