Electrochemical Activation of Diverse Conventional Photoredox Catalysts Induces Potent Photoreductant Activity

Herein, we disclose that electrochemical stimulation induces new photocatalytic activity from a range of structurally diverse conventional photocatalysts. These studies uncover a new electron‐primed photoredox catalyst capable of promoting the reductive cleavage of strong C(sp2)−N and C(sp2)−O bonds. We illustrate several examples of the synthetic utility of these deeply reducing but otherwise safe and mild catalytic conditions. Finally, we employ electrochemical current measurements to perform a reaction progress kinetic analysis. This technique reveals that the improved activity of this new system is a consequence of an enhanced catalyst stability profile. Electrochemical activation of conventional photocatalysts induces potent photoreductant activity. These studies resulted in the discovery of an electron‐primed photoredox catalyst capable of cleaving strong aryl C−N and C−O bonds to aryl radical intermediates. Mechanistic experiments revealed that enhanced activity relative to previously developed electron‐primed photoredox systems was a result of improved catalyst stability.