Photoredox‐Catalyzed Dimerization of Arylalkenes via an Oxidative [4+2] Cycloaddition Sequence: Synthesis of Naphthalene Derivatives

We report a radical cation [4+2] annulation of arylalkenes to afford naphthalene derivatives using an organic photosensitizer (9‐mesityl‐10‐methylacridinium perchlorate) under visible light photocatalysis. In the presence of oxygen (in the air), the oxidative dimerization/intramolecular [4+2] cycloaddition of two alkene molecules provides 3,4‐dihydronaphthalen‐1(2 H )‐ones in good to high yields. Under a nitrogen atmosphere, (dihydro)naphthalenes were attained in moderate to excellent yields by using Selectfluor as the oxidant. The transformation proceeds via a tandem dimeric electrophilic addition/Friedel–Crafts cyclization/radical coupling/elimination sequence. This approach represents a mild and straightforward assembly of the naphthalene skeleton using a visible light photocatalytic cascade strategy. magnified image