However, in order to find new applications and access unexplored regions of chemical space, alternative reactivity modes that harness the unique properties of BCBs are required. In 1979, Gassman reported a study on the relationship between alkyl substitution and the ease of oxidation of strained hydrocarbons . By measuring the half-wave potentials of a variety of substituted bicyclo[1.1.0]butanes, it was demonstrated that the σ-framework of the bicycle could readily undergo single-electron oxidation to the corresponding radical cation (Fig. ) . Despite this discovery, the synthetic potential of bicyclo[1.1.0]butyl radical cations has been severely underexplored , with non-selective nucleophilic ring-opening being the only transformation demonstrated for these intermediates . We therefore determined to assess the feasibility of single-electron oxidation as a strategy to access new bicyclo[1.1.0]butane reactivity.