Macromolecular Photoediting Using Single-Electron Logic

Accessing the chemistry of reactive intermediates under mild conditions has significantly expanded the available chemical space for molecular transformations. Nowhere is this more apparent than in the context of photoredox catalysis. Despite abundant literature precedents for using this powerful methodology to build complex targets, there are comparatively few reports that leverage photoredox catalysis for macromolecular editing. Here, we report a mild photoredox approach that enables both the functionalization and degradation of polyalkenamers to valuable feedstocks. Irradiation with visible light (including natural sunlight) in the presence of a pyrillium photoredox catalyst promoted facile chain scission in a variety of substrates. This metal-free approach transformed high molar mass materials (>300 kDa) to low molar mass species (<15 kDa) within 10 min. Moreover, we could completely degrade macromolecules into a range of useful targets (C₁₆-C₂₉ species) within 96 h. Mechanistic and kinetic experiments were carried out to understand this reactivity, which could be coupled with hydrofunctionalizations to create tailored products.