In mechanochemistry, molecules under tension can react in unexpected ways. The reactivity of mechanophores (mechanosensitive molecules) can be controlled using various geometric or electronic factors. Often these factors affect the rate of mechanical activation but sometimes give rise to alternative reaction pathways. Here we show that a simple isotope substitution (H to D) leads to a reversal of selectivity in the activation of a mechanophore. Remarkably this isotope effect is not kinetic in nature but emerges from dynamic effects in which deuteration reduces the ability of the reactant to follow a post-transition-state concerted trajectory on the bifurcated force-modified potential energy surface. These results give a new insight into the reactivity of molecules under tension.