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, we 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 exhibited broad substrate accommodation and gave the corresponding products in high yields and selectivity.