External double bonds of five-, six-, seven-membered rings as well as simple acyclic trisubstituted alkenes were all nitrated to give rise to tertiary nitroalkanes. Cyclic internal alkenes (42-44, 53-54) can also be enlisted. Compounds such as the tertiary nitroalkane 39 bearing a four-carbon ester subunit are generally prepared through laborious and somewhat dangerous protocols originating from secondary nitroalkanes. For instance, after preparing the requisite nitroalkane, base-promoted Michael addition followed by Arndt-Eistert homologation (requiring diazomethane, See SI) is required. In contrast, 39 is easily accessed in two steps from the commercial ketone (Wittig followed by alkene hydronitration). The utility of this transformation in a more complex settings was also pursued. Thus, alkenes derived from drugs and natural products were subjected to the conditions, leading to the formation of desired tertiary nitroalkanes (58-66) in good to excellent yields. In particular, diverse multi-substituted (hetro)arenes, esters, tertiary amines, electron rich arenes, and sulfonamides were found to be compatible with the reaction conditions, indicating the potential application of this reaction in late-stage nitration of complex contexts. It is worth noting that none of the compounds depicted in Table have been prepared before and 14 of them were unambiguously confirmed by X-ray crystallographic analysis. In terms of limitations, this method is best suited towards the preparation of tertiary nitro compounds. Using simple terminal olefins results in ca. 20% yield of secondary alkyl nitro compounds (see SI for details) with the mass balance being reduced olefin.