Formal Higher‐Order [8 + 3] Cycloaddition of Azaheptafulvenes with Donor–Acceptor Cyclopropanes

Cyclohepta[ b ]pyridine derivatives have attracted significant attention owing to their unique bioactivities. Herein, the authors describe an efficient method to access various cyclohepta[ b ]pyridine derivatives through formal higher‐order [8 + 3] cycloaddition of azaheptafulvenes with donor–acceptor cyclopropanes catalyzed by Yb(OTf) 3 . This method exhibits broad substrate accommodation and gives the corresponding products in high yields and selectivity.