Stereoelectronic Effects in Force-Accelerated Retro-Diels–Alder Reactions

Abstract In polymer mechanochemistry, mechanosensitive molecules (mechanophores) are activated upon elongation of anchored arms. The reactivity a mechanophore can be influenced by variety structural factors, including the geometry attachment arms and nature eventual substituents. Here we investigate stereoelectronic effects in force-accelerated Diels–Alder reactions using CoGEF (Constrained Geometries simulate External Force) calculation method. We found that presence an electron-donating heteroatom on diene leads to lower activation force, mechanochemical is suppressed when anchor group attached central rather than lateral position.