Hu Jiefeng, Zhang Kun, Wang Jing, Huang Mingming, Chen Shuangru, Shi Zhuangzhi, Marder Todd B
State Key Laboratory of Flexible Electronics (LoFE) & Institute of Advanced Materials (IAM), Nanjing University of Posts & Telecommunications Nanjing 210023 China
School of Chemistry and Molecular Engineering, Nanjing Tech University Nanjing 211816 China.
Chem Sci. 2025 May 12. doi: 10.1039/d5sc02670a.
The application of -diboryl cyclopropanes as versatile building blocks for enhancing molecular complexity has been limited, despite the availability of a few synthetic methods. Herein, we disclose a practical and versatile manganese-catalyzed protocol that enables the synthesis of -di(boryl)cyclopropanes from non-activated alkenes in combination with (diborylmethyl)iodides. This photoinduced strategy displays good functional-group tolerance, and encompasses a wide range of applicable substrates, making it applicable to the late-stage modification of natural products. Mechanistic experiments suggest that the reaction proceeds an intermolecular halogen-atom transfer radical addition, followed by deprotonative alkylation with lithium diisopropylamide, ultimately yielding cyclization products. The versatility and practicality of this approach are further highlighted by the successful implementation of several transformations, which provide an expedited route for synthesizing highly functionalized molecules.
尽管有几种合成方法，但作为用于提高分子复杂性的通用结构单元，-二硼基环丙烷的应用一直受到限制。在此，我们公开了一种实用且通用的锰催化方案，该方案能够将非活化烯烃与（二硼基甲基）碘化物结合，合成-二（硼基）环丙烷。这种光诱导策略具有良好的官能团耐受性，涵盖了广泛的适用底物，使其适用于天然产物的后期修饰。机理实验表明，该反应通过分子间卤原子转移自由基加成进行，随后用二异丙基酰胺锂进行去质子化烷基化，最终生成环化产物。通过成功实施几种转化，进一步突出了该方法的通用性和实用性，这些转化为合成高度官能化的分子提供了一条快捷途径。
