C(sp 3 )-F Bond Activation by Lewis Base-Boryl Radicals via Concerted Electron-Fluoride Transfer.

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.
(© 2024 Wiley-VCH GmbH.)