Visible‐Light‐Driven Synthesis of 2‐Acyl‐3‐Arylnaphthofurans via Photoredox/Selenium‐Catalyzed 3,3‐Rearrangement/Cyclization of Propargylic Aryl Ethers

A visible‐light‐driven, synergistic photoredox/selenium dual catalytic system has been developed for the synthesis of 2‐acyl‐3‐arylnaphthofurans. Utilizing readily accessible propargylic aryl ethers, this transformation proceeds via a 3,3‐rearrangement/cyclization cascade under mild conditions. This protocol exhibits a broad substrate scope and excellent functional group tolerance, efficiently affording the target 2‐acyl‐3‐arylnaphtho‐ or benzofurans in moderate to good yields. The synthetic utility of the method is further highlighted by diverse downstream transformations of the products. Based on mechanistic investigations, a plausible pathway is proposed to elucidate the reaction process. This strategy provides a practical and sustainable alternative to traditional approaches for accessing biologically relevant naphthofuran, benzofuran, and naphthothiophene scaffolds.