通过协同电子-氟转移实现路易斯碱-硼基自由基对C(sp)-F键的活化
C(sp)-F Bond Activation by Lewis Base-Boryl Radicals via Concerted Electron-Fluoride Transfer.
作者信息
Guo Xueying, Zhang Yuchen, Lai Xiaoyu, Pang Yubing, Xue Xiao-Song
机构信息
Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials and Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 20032, China.
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Center for Ultrafast Science and Technology, Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, China.
出版信息
Angew Chem Int Ed Engl. 2025 Jan 15;64(3):e202415715. doi: 10.1002/anie.202415715. Epub 2024 Nov 16.
Selective C-F bond activation through a radical pathway in the presence of multiple C-H bonds remains a formidable challenge, owing to the extraordinarily strong bond strength of the C-F bond. By the aid of density functional theory calculations, we disclose an innovative concerted electron-fluoride transfer mechanism, harnessing the unique reactivity of Lewis base-boryl radicals to selectively activate the resilient C-F bonds in fluoroalkanes. This enables the direct abstraction of a fluorine atom and subsequent generation of an alkyl radical, thus expanding the boundaries of halogen atom transfer reactions.
在存在多个碳氢键的情况下，通过自由基途径实现选择性碳氟键活化仍然是一项艰巨的挑战，这是由于碳氟键极强的键能。借助密度泛函理论计算，我们揭示了一种创新的协同电子-氟转移机制，利用路易斯碱-硼基自由基的独特反应性来选择性活化氟代烷烃中稳定的碳氟键。这使得能够直接夺取一个氟原子并随后生成烷基自由基，从而拓展了卤原子转移反应的边界。
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