Dearomative Ring Expansion of Polycyclic Arenes

Benzocycloheptenes constitute a common structural motif embedded in many natural products and biologically active compounds. Herein, we report their concise preparation from non‐activated polycyclic arenes using a two‐step sequence involving dearomative [4+2]‐cycloaddition with arenophile in combination with palladium‐catalyzed cyclopropanation, followed by cycloreversion‐initiated ring expansion. The described strategy provides a working alternative to the Buchner reaction, which is limited to monocyclic arenes. Overall, this methylene‐insertion molecular editing approach enables rapid and direct conversion of simple (hetero)arenes into a range of substituted (aza)benzocycloheptatrienes, which can undergo a myriad of downstream functionalizations.