Recently, we have reported carbamoyloximes as a new mechanophore class to protect latent amines. We have shown that carbamoylaldoximes undergo force-induced homolytic bond scission at the N-O oxime bond where one chain fragment radical decarboxylates to yield the free amine and the other forms a nitrile (Figure , AO pathway). We hypothesize that the introduction of alkyl substituents R in the αposition of the oxime moiety may affect its mechanochemical reactivity twofold: (i) steric perturbation and elongation of the oxime bond and (ii) electronic stabilization of the mechanochemically formed iminyl radical by hyperconjugation. We speculate that both effects will increase the mechanochemical reactivity of the carbamoyloxime motif by lowering the necessary activation energy Ea. Here we show that these carbamoylketoximes undergo force-induced N-O scission just as carbamoylaldoximes, but afford a final ketone due a different radical pathway (Figure , MKO and TKO pathways). We demonstrate that carbamoylketoximes show increased mechanochemical reaction rates compared to their aldoxime counterparts and that this rate increase correlates with the degree of substitution on the α-substituent R. Surprisingly, we find that the thermal and photochemical stabilities of carbamoyloximes increase as well with the introduction of the α-substituent, suggesting diverging reaction trajectories on the zero-force and on the force-modified potential energy surface, which we uncover using combined experimental and computational techniques. Thereby, we present a counterintuitive example of a non-pericyclic mechanophore class where both mechanochemical reaction rate and thermal stability increase together, which may serve as a mechanistic example for future systematic mechanophore discoveries.