Remote Functionalization of Inert C(sp3)–H Bonds via Dual Catalysis Driven by Alkene Hydrofluoroalkylation Using Industrial Feedstocks

Abstract

We have developed a dual-catalytic system capable of site-selective azidation of inert C(sp³)–H bonds with concomitant and modular anti-Markovnikov alkene fluoroalkylation. The protocol leverages the synergetic cooperation of both the photocatalyst and earth-abundant iron catalyst to deliver two radical species in succession to minimally functionalized alkenes. This powerful catalyst system exhibits broad scope, mild conditions, and excellent regioselectivity for a variety of substrates and fluoroalkyl fragments. The key to this C-centered radical relay is the matched rate of both photocatalytic and iron catalytic cycles, ensuring selective azidofluoroalkylation with a broad array of fluoroalkyl sources from trivial reagents.