Force-induced Transition State Rupture Enables Mechanistic Control in Aziridine Mechanochemistry

Abstract

Besides long established thermal and photochemical activation of chemical reactivity, mechanical forces emerged as a further tool to drive reactions. Molecular motifs which undergo particular transformations under external force, so called mechanophores, are oftentimes small cyclic structures which can easily be activated due to their inherent ring strain. In the ring-opening of cis-substituted 4 π-electron mechanophores, the pulling force activates the Woodward-Hoffmann-forbidden disrotatory reaction, which can compete with the allowed conrotatory reaction. We introduce the concept of transition state rupture, a force-induced catastrophe which results in changing the preferred reaction pathway on the force-modified potential energy surface, controlling selectivity. By computing force-modified stationary points and reaction pathways for various linker-mechanophore combinations we rigorously investigate how the magnitude of the external force determines the mechanochemical mechanism. Using the concept of transition state rupture, we explain previous observations made in sonication experiments studying the activation of aziridine mechanophores, elucidating the reaction mechanisms and product selectivity.