C(sp)-F Bond Activation by Lewis Base-Boryl Radicals via Concerted Electron-Fluoride Transfer.

Angew Chem Int Ed Engl

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.

Published: January 2025

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.

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http://dx.doi.org/10.1002/anie.202415715DOI Listing

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