Aliphatic nitro-containing structures are found in a variety of materials such as medicines, agrochemicals, energetics, natural products, and key building blocks. Tertiary nitroalkanes, in particular, are useful functional groups as outlined in Figure . For instance, pyrrolidine 3 exhibits a dramatic difference in biological activity relative to 2, compound 4 has been used as a key intermediate towards rolapitant, and molecules 5 -6 have been derived or found from natural sources. Conventional routes to tertiary nitro compounds generally rely on polar-bond disconnections as outlined in Figure . Thus, anionic reactions of secondary nitro compounds (7) using strong base or potent electrophiles under transition metal or enzymatic catalysis 10 are commonly employed.