Intramolecular Dearomative [2 + 2] Cycloaddition of (Hetero)arenes via Energy Transfer Catalysis: Exploration of Divergent Three-Dimensional Skeleton Editing

Dearomative [2 + 2] cycloadditions offer a powerful route for converting planar arenes into complex three-dimensional (3D) scaffolds prevalent in bioactive molecules. Herein, we report an intramolecular dearomative [2 + 2] cycloaddition of <i>N</i>-acryloyl-<i>N</i>-substituted α/β-naphthamides and benzoheterocycles, driven by visible-light energy transfer catalysis. This strategy effectively overcomes the high energetic barrier of dearomatization, facilitating the construction of synthetically valuable, strained fused-ring systems with divergent 3D architectures. The reaction exhibits a broad substrate scope and excellent functional group tolerance. Mechanistic investigations uncover a retro-cycloaddition pathway that divergently generates two structurally distinct fused-ring skeletons: direct ring-closure and cross ring-closure products, with the former predominating initially. This work not only provides a novel method for 3D skeleton editing but also highlights the potential of energy transfer catalysis in constructing complex molecular architectures.