Photon-Primed Organic Electrosynthesis Enabled by Oxidation of Photon-Induced Intermediates

We present a catalyst-free strategy that combines photochemical and electrochemical activation to unlock unique reactivity in otherwise less reactive molecules. Photochemical excitation generates intermediates that can undergo electrochemical oxidation to form highly electrophilic species that can engage weak nucleophiles, enabling the synthesis of diverse heterocycles under mild conditions. Mechanistic studies, including voltammetric, spectroscopic, and computational analyses, suggest that a light-driven redox chain mechanism plays a crucial role, significantly enhancing the apparent Faradaic efficiency (>100%). The broad substrate scope including bioactive scaffolds highlights the potential of this approach to expand the reactivity landscape in electrochemical synthesis.