Radical 1,4/5‐Amino Shift Enables Access to Fluoroalkyl‐Containing Primary β(γ)‐Aminoketones under Metal‐Free Conditions

Abstract A novel radical 1,4/5‐amino shift from the oxygen center of alkene‐tethered diphenyl ketoxime ethers to the carbon center to achieve high value‐added fluoroalkyl‐containing primary β(γ)‐amino‐ketones is reported. Mechanism studies reveal that the migration is triggered by the alkene addition of fluoroalkyl radical derived from the electron donor‐acceptor (EDA) complex of Togni's reagent II or fluoroalkyl iodides and quinuclidine, and involves a unique 5(6)‐exo‐trig cyclization of the carbon‐centered radical onto the N‐atom of ketoxime ethers followed by a cascade sequence of N−O bond cleavage and dehydrogenation. Notably, besides Togni's reagent II and fluoroalkyl iodides, this protocol is also compatible with other radical precursors to provide various functionalized primary aminoketones.