Furan Release via Force-Promoted Retro-[4+2][3+2] Cycloaddition

Abstract

Mechanophores (mechanosensitive molecules) have been instrumental in the development of various force-controlled release systems. However, the release of functional organic molecules is often the consequence of a secondary (nonmechanical) process triggered by an initial bond scission. Here we present a new mechanophore, built around an oxanorbornane-triazoline core, that is able to release a furan molecule following a force-promoted double retro-[4+2][3+2] cycloaddition. We explored this unprecedented transformation experimentally (sonication) and computationally (DFT, CoGEF) and found that the observed reactivity is controlled by the geometry of the adduct, as this reaction pathway is only accessible to the endo-exo-cis isomer. These results further demonstrate the unique reactivity of molecules under tension and offer a new mechanism for the force-controlled release of small molecules.