Amidyl Radicals by Oxidation of α-Amido-oxy Acids: Transition-Metal-Free Amidofluorination of Unactivated Alkenes

Article abstract of DOI:10.1002/anie.201804966

A three-component transition-metal-free amidofluorination of unactivated alkenes and styrenes is presented. α-Amido-oxy acids are introduced as efficient and easily accessible amidyl radical precursors that are oxidized by a photoexcited organic sensitizer (Mes-Acr-Me) to the corresponding carboxyl radical. Sequential CO₂ and aldehyde/ketone fragmentation leads to an N-centered radical that adds to an alkene. Commercial Selectfluor is used to trap the adduct radical through fluorine-atom transfer. The transformation features by high functional-group tolerance, broad substrate scope, and practical mild conditions. Mechanistic studies support the radical nature of the cascade.