Photoinduced Ring‐Opening Functionalization of α‐Imino‐Oxy Acids and Alkanols Enabled by Phthalate‐Derived Proton‐Coupled Electron Transfer Mediator

Comprehensive Summary A dual catalytic manifold that combines photoredox catalysis and phthalate‐catalyzed hydrogen‐atom abstraction process has been developed to realize diverse fragmentation‐functionalization reactions. Key to success is photocatalytic generation of tether‐tunable distonic radical anions (TDRAs) as proton‐coupled electron transfer mediators, enabling polarity‐matching‐based formation of heteroatom‐centered radicals that allows for further controlled exploration of chemical space via C–C β ‐scission. These reactions feature exceptionally broad substrate generality, gram‐scale synthesis, potential biocompatibility and late‐stage modification of complex molecules, while obviating the use of stoichiometric and often unsafe peroxides in our previous studies. Mechanistic studies support a redox‐neutral radical relay pathway enabled by in situ ‐generated, catalytic TDRAs.