Electroreductive Intramolecular Heck‐Type Cyclization for the Synthesis of Benzofused Oxygenated Heterocycles

Conventional synthetic routes to benzofused oxygenated heterocycles, such as Dihydrobenzofuran, chromane and isochromane derivatives, often involve complex synthetic conditions, high costs, and environmental concerns. The key to addressing this challenge lies in achieving transition‐metal‐free C(sp²)–I bond cleavage to enable intramolecular radical cyclization. Inspired by electroreductive strategies, we developed a convenient, transition‐metal‐free electroreductive tandem reaction for synthesizing dihydrobenzofuran, chromane, and isochromane derivatives. Comprehensive evaluation demonstrates that our approach not only simplifies synthetic conditions but also suppresses competing hydrogenation and halogenation pathways at the exocyclic carbon radical center.