Silver‐Catalyzed Three‐Component Radical Aminofluorination of Arylalkenes with Selectfluor and Amino <i>N</i> ‐Heterocycles

A silver‐catalyzed three‐component radical aminofluorination of arylalkenes has been developed, utilizing free N ‐heterocyclic amines and Selectfluor as key reagents. Under mild conditions, a diverse array of β‐fluoroamine derivatives were obtained in moderate to excellent yields (up to 98%). The protocol exhibits broad substrate scope, tolerating various functional groups such as halogens, alkyls, esters, and cyano groups on both the amino heterocycle and alkene components. Mechanistic studies support a radical pathway involving silver‐mediated oxidation of the amino heterocycle to generate an amino radical, followed by addition to the alkene and subsequent fluorine atom transfer. This method provides a straightforward route to valuable monofluoroalkylated amino N ‐heterocycles.