Six of the nine current oxetane-containing clinical candidates are substituted in the 3-position with an amine functional group, whereby the oxetane plays a crucial role to reduce basicity of the amine to appropriate levels. Consequently, the application of oxetanes as analogues of benzylic amines may have advantages in controlling pKa as well as affecting metabolism at benzylic sites. Benzodioxole is a scaffold frequently seen across natural products and approved medicines, and several oxetane analogues of marketed drugs containing benzylic amines were efficiently accessed from benzodioxole OSF 7. Analogues of fipexide (21), piribedil (22), fenoverine (23) and medibazine (24) were all prepared directly by reacting the suitable amine nucleophiles under the deFS conditions (Scheme 1b).