Photoinduced Ring-Opening Functionalization of α-Imino-Oxy Acids and Alkanols Enabled by Phthalate-Derived Proton-Coupled Electron Transfer Mediator
Chao Tian , Lei Shi
Chinese Journal of Chemistry ›› 2025, Vol. 43 ›› Issue (16) : 1988 -1996.
Photoinduced Ring-Opening Functionalization of α-Imino-Oxy Acids and Alkanols Enabled by Phthalate-Derived Proton-Coupled Electron Transfer Mediator
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.
Tether-tunable distonic radical anions / Heteroatom–H bond activation / Photoredox catalysis / Cross-coupling / α-Imino-oxy acids / Alcohols / Radical reactions / Synthetic methods
2025 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
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