Our initial strategy for the synthesis of substituted spirocyclohexyl piperidine nitroxides relied on classical enolate chemistry (Scheme 1). Spirocyclohexyl piperidinone 3 was prepared from the commercially available 2,2,6,6-tetramethylpiperidinone according to a literature procedure. Deprotonation of 3 with LDA, followed by alkylation with methyl iodide, resulted in the monomethylated product 4 in moderate yield. Subsequent oxidation with m-CPBA provided nitroxide radical 5 in 84% yield. As radical 5 is crystalline, we investigated its three-dimensional structure by X-ray crystallography to reveal the conformational effect of a single substituent on the nitroxide ring. The solid-state structure (Scheme 1) indicates that the methyl group adopts an axial orientation, with the nitroxide ring preferring a twist-boat conformation. This permits the spirocyclic scaffold to maintain an overall open arrangement.