Transition‐Metal‐Free Trifluoromethylaminoxylation of Alkenes

No transition metal! Fluorinated hypervalent-iodine reagents react with TEMPONa in the presence of an alkene under mild conditions to give the corresponding perfluoroalkylaminoxylation products. These radical addition/trapping reactions occur with high stereoselectivity using commercially available reagents, and the product alkoxyamines are readily transformed into the corresponding alcohols.