We have shown that insertion of the imino fragment into the key bond-breaking step of the well-established epoxide ring-closure process results in a transition state that delivers a novel iminologous fragmentation reaction to afford tetra-substituted epoxides. The mechanism has been examined, and it was proposed that the reaction is stereospecific and follows a concerted ring-closure pathway. We anticipate the application of the principle of iminology in other established processes to further demonstrate that structural modification of reactive intermediates can be used as a strategy in the development of new transformations.