Sequential σ‑Bond Insertion/Benzannulation Involving Arynes: Selective Synthesis of Polysubstituted Naphthalenes

An interesting σ-bond insertion/benzannulation reaction for the synthesis of polysubstituted naphthalene derivatives has been developed from readily accessible ketones, arynes, and alkynoates. This practical and transition-metal-free method provides a novel route to diverse naphthalenes through a substrate-controlled rearrangement reaction with the cleavage of C–C bonds.