Remote Functionalization\nof Inert C(sp<sup>3</sup>)–H Bonds via Dual Catalysis Driven\nby Alkene Hydrofluoroalkylation\nUsing Industrial Feedstocks

We have developed a dual-catalytic system capable of\nsite-selective\nazidation of inert C(sp<sup>3</sup>)–H bonds with concomitant\nand modular anti-Markovnikov alkene fluoroalkylation. The protocol\nleverages the synergetic cooperation of both the photocatalyst and\nearth-abundant iron catalyst to deliver two radical species in succession\nto minimally functionalized alkenes. This powerful catalyst system\nexhibits broad scope, mild conditions, and excellent regioselectivity\nfor a variety of substrates and fluoroalkyl fragments. The key to\nthis C-centered radical relay is the matched rate of both photocatalytic\nand iron catalytic cycles, ensuring selective azidofluoroalkylation\nwith a broad array of fluoroalkyl sources from trivial reagents.