Polymer mechanochemical pericyclic reactions are reviewed with regard to their structural features and substitution prerequisites to the polymer framework.

The attachment point of the polymer chain to a force-responsive molecular unit (mechanophore) is a decisive parameter determining bond scission rate and ultimately the mechanochemical reaction outcome. However, such regiochemical polymer substituent effects have not yet been investigated for 9-πextended anthracene-maleimide Diels-Alder adducts. Here we combine three methods, namely ultrasonication, CoGEF computation, and flow activation, to understand the influence of the pulling point location on the mechanochemical reactivity of this mechanophore class. We find minor mechanochemical reactivity differences between the investigated constitutional mechanophore isomers. Concomitantly, our results highlight the capabilities and limitations of the employed experimental techniques for such delicate variances and raise the question whether these are relevant for mechanochemical applications in a material context.

Mechanophores are molecular moieties that are incorporated into polymers and respond to force with constitutional, configurational, or conformational bond rearrangements to enable functionality. Up to today, several chemically latent motifs have been activated by polymer mechanochemical methods, but the generation of secondary amines remains elusive. Here we report carbamoyloximes as mechanochemical protecting groups for secondary amines. We show that carbamoyloximes undergo force‐induced homolytic bond scission at the N−O oxime bond in polymers thus producing the free amine, as the reaction proceeds via the carbamoyloxyl and aminyl radicals, analogously to its photochemical counterpart. Eventually, we apply the carbamoyloxime motif in a force‐activated organocatalytic Knoevenagel reaction. We believe that this protecting strategy can be universally applied for many other secondary and primary amines in polymer materials.