Dearomatizing Photocyclization and Oxidative Aromatization: Constructing Polycyclic Arenes from Styrenes.

The direct construction of polycyclic arenes through ring formation using simple building blocks is highly appealing but remains challenging in organic chemistry. In this study, we introduce an efficient cascade reaction that combines dearomatizing photocyclization with oxidative aromatization, driven by organophotocatalysis. Conducted under mild, transition-metal-free conditions, this reaction seamlessly converts styrene derivatives into a diverse array of functionalized polycyclic aromatic compounds with good yields and regioselectivity. This approach provides a straightforward and economical route to valuable polycyclic arenes, starting from readily available and abundant styrene derivatives.