Efficient Access to Polycyclic Scaffolds via a Dearomatization/Polyene Cyclization Cascade

Herein, we report a hypervalent iodine‐mediated tandem reaction that synergistically integrates phenol dearomatization with polyene cyclization for the efficient construction of complex polycyclic frameworks. This method enables the one‐step stereoselective synthesis of trans ‐benzo[ f ]isoquinoline and spirocyclohexadienone skeletons. The reaction proceeds rapidly under mild conditions, delivering products in high yields with excellent diastereoselectivity. This work not only expands the application of hypervalent iodine reagents in organic synthesis but also provides a novel and efficient strategy for accessing polycyclic natural product scaffolds.