We hypothesized that an exocyclic methylene group could induce spirocyclic pyrrolidinyl nitroxides to adopt closed conformations, in analogy to our previous work. To access this scaffold, we devised a synthetic route relying on a Johnson-Claisen rearrangement (Scheme 1). A similar strategy has previously been demonstrated with less sterically congested tetramethylsubstituted nitroxides. The synthesis began with commercially available 2,2,6,6-tetramethyl-4-piperidone 1, which can be transformed into the spirocyclic equivalent 2 via a previously described ketone exchange method. Ring contraction was accomplished through dibromination of ketone 2 and subsequent treatment of the dibrominated hydrobromide salt 3 with freshly prepared sodium methoxide, resulting in a Favorskii rearrangement to pyrroline methyl ester 4. Amine oxidation with metachloroperbenzoic acid (m-CPBA) led to the formation of nitroxide 5, and the ester was reduced to the allylic alcohol 6 using diisobutylaluminium hydride (DIBAL-H). This key intermediate was heated in the presence of triethyl orthoacetate and catalytic acid, resulting in a thermal Johnson-Claisen rearrangement to the exo-methylene substituted pyrrolidine nitroxide ethyl ester 7 in excellent yield.