Overall, we present protocols for the preparation of 3,3-substituted thietane dioxides through the formation of carbocation intermediates. The application of increased temperatures was important to minimise formation of a thiete dioxide. We expect thietane dioxides to see broader application in medicinal chemistry with the development of new methods for their preparation, and the increase in commercial availability. This methodology provides a rapid and divergent approach to these disubstituted derivatives, and form C-C, C-S and C-O bonds directly onto the intact 4-membered ring. The thietane dioxide rings display high chemical stability and are suitable for application in further cross-coupling and derivatisation reactions.