Non-Innocent Radical Ion Intermediates in Photoredox Catalysis: Parallel Reduction Modes Enable Coupling of Diverse Aryl Chlorides

10 June 2021, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


We describe a photocatalytic system that elicits potent photoreductant activity from conventional photocatalysts by leveraging radical anion intermediates generated in situ. The combination of isophthalonitrile and sodium formate promotes diverse aryl radical coupling reactions from abundant but difficult to reduce aryl chloride substrates. Mechanistic studies reveal two parallel pathways for substrate reduction both enabled by a key terminal reductant byproduct, carbon dioxide radical anion.


Photoredox Catalysts
electron-primed photoredox catalysis
Aryl Radicals

Supplementary materials

Non-innocent radical ion intermediates in photoredox catalysis–SI


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