Oxoammonium salts are commonly used for oxidations of alcohols to aldehydes and ketones (N. Merbouh, J. M. Bobbitt, C. Bruckner, Org. Prep. Proc. Int. 2004, 36, 1). Our focus was to investigate the reactions of 2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluroborate (1) with isolated alkenes. Selective reaction of nonactivated trisubstituted alkenes with 1 to give alkoxyamines (2) in an ene-like fashion will be discussed. Alkoxyamines, which are widely used as polymer initiators, can be synthesized directly from nonactivated alkenes without the use of heavy metals by this method. Reaction of 1 with activated benzene ring systems, such as 1,3,5-trimethoxybenzene, will also be discussed.