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

Abstract

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.