Spirocyclization-Enabled Remote Phosphorothiolation of Nonactivated Arenes via Dual Photoredox/Copper-Catalyzed Dearomatization

Spirocyclic frameworks are key structural motifs in bioactive molecules, driving ongoing efforts to develop efficient and sustainable synthetic methods. Herein, we report a synergistic photocatalysis/copper dual-catalytic system that enables direct dearomative spirocyclization via the simultaneous incorporation of phosphorothioate groups in a single synthetic operation. This strategy allows rapid, selective construction of complex spirocenters from simple nonactivated aromatic precursors, exhibits broad substrate scope, including bioactive relevant scaffolds, and provides a robust platform for diversity-oriented synthesis with significant potential in drug discovery.