Direct Construction of Fused/Bridged 3D Rings via Visible‐Light Induced Dearomative Cycloaddition of Arenes

Abstract Three‐dimensional aliphatic fused and bridged rings are key pharmacophores in drugs and bioactive natural products. Here, we reported an organocatalytic visible‐light induced dearomative cycloaddition of (hetero)arenes, with organic light‐emitting diode material 4CzIPN or readily accessible thioxanthone as photocatalyst. A series of cyclobutane‐fused polycyclic structures and bridged bicyclo scaffolds were prepared in reasonable yields (27–99% yield) with medium to excellent diastereoselectivity (1.4:1 to>20:1 dr ), predictable regioselectivity, good functional group compatibilities and broad substrate scopes. The combination of experimental and computational studies supported the energy transfer pathways. magnified image