Photoinduced Vinylogous Dearomatization

The first vinylogous dearomatization is reported. Under a photoinduced platform, various benzothiophenes functionalized by ketones at the 3-position could react with 3-methylenechroman-4-ones efficiently, leading to a variety of valuable products that contain the pharmaceutically significant chromones and 2,3-dihydrobenzo[b]thiophenes concurrently. The transformations were revealed to experience hydrogen-atom transfer, dearomatization, olefin migration, and radical cross coupling.