Reaction of various alkenes with commercially available N-fluorobenzenesulfonimide (NFSI) and TEMPONa provides the corresponding aminooxygenation products in moderate to good yields. Single electron transfer from readily generated TEMPONa to NFSI allows for clean generation of the corresponding bissulfonylamidyl radical along with TEMPO. N-radical addition to an alkene and subsequent TEMPO trapping provides the corresponding aminooxygenation product.