C(sp³)−F Bond Activation by Lewis Base‐Boryl Radicals via Concerted Electron‐Fluoride Transfer

Abstract

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.