AbstractThe chemistry of 2,2,4,4‐substituted pentane derivatives has been investigated with the aim of providing a flexible and versatile synthetic route to pyrimidinyl nitronyl nitroxides, in which the bis‐N‐oxy fragment is incorporated in a six‐membered ring. The synthesis of 2,4‐diamino‐2,4‐dimethylpentane and 2,4‐bis(hydroxylamino)‐2,4‐dimethylpentane, convenient precursors of these nitroxides, is described and full characterization of a series of pyrimidinyl nitronyl nitroxides is reported, along with a preliminary study of their coordination properties.