Dearomative Ring Expansion of Polycyclic Arenes

Paolo Piacentini, Tanner W. Bingham, David Sarlah

Research output: Contribution to journalArticlepeer-review


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.

Original languageEnglish (US)
Article numbere202208014
JournalAngewandte Chemie - International Edition
Issue number36
StatePublished - Sep 5 2022


  • Arenophiles
  • Benzocycloheptatrienes
  • Buchner Reaction
  • Dearomatization
  • Ring Expansion

ASJC Scopus subject areas

  • General Chemistry
  • Catalysis


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