Expanding the Reactivity of Donor-Acceptor Cyclopropanes: Synthesis of Benzannulated Five-Membered Heterocycles via Intramolecular Attack of a Pendant Nucleophilic Group

Lewis-acid-induced domino transformations of donor-acceptor cyclopropanes, possessing a nucleophilic center embedded in a donor group, into functionalized 2,3-dihydrobenzo[b]furans and 2,3-dihydrobenzo[b]thiophenes are reported herein. An unusual switch of the electrophilic center in the three-membered ring, from the atom bearing a donor substituent to an unsubstituted carbon atom, was achieved by a judicious choice of Lewis acid, which induces the isomerization of a cyclopropane to an electrophilic alkene, and the length of linker, connecting a nucleophilic moiety and the small ring. © 2018 American Chemical Society.