The Diels–Alder reaction of pyrroles and arynes generated from ortho-diiodoarenes and NaH

Nitrogen-containing polycyclic structures are core motifs in a range of biologically active compounds and organic functional materials, but efficient access to these benzofused skeletons from simple starting materials remains a challenge for synthetic chemists. In this work, we develop a practical intermolecular Diels–Alder reaction between arynes generated in situ from o-diiodoarenes and sodium hydride, and various substituted pyrroles. The transformation proceeds under relatively mild conditions to construct polycyclic N-bridged frameworks efficiently, with broad substrate tolerance for both coupling partners. A gram-scale experiment confirmed the good scalability of this protocol, and the obtained cycloadduct can be readily derivatized to a useful naphthylamine derivative, demonstrating the high synthetic utility of this method.