Substrate‐Controlled Dearomative Cycloadditions of Perfluoronaphthalenes via Visible‐Light Energy Transfer Catalysis: Switchable Access to [2+2], [4+2], and Diastereoconvergent Cycloadducts

We report the first substrate‐controlled intermolecular dearomative cycloaddition of polyfluoronapthalenes in which the substitution pattern of the olefin coupling partner governs the mode of cycloaddition. Under visible‐light energy transfer ( VL EnT) catalysis, monosubstituted olefins react with octafluoronaphthalene to give dual dearomative ortho [2+2] cycloadducts selectively. In comparison, 1,1‐disubstituted olefins afford the corresponding para [4+2] cycloadducts with complete regiospecificity under otherwise identical conditions. Trisubstituted olefins engage in a diastereoconvergent [4+2] cycloaddition, delivering a single diastereomeric product regardless of the olefin geometry. This mild, operationally simple strategy provides direct access to structurally diverse, perfluorinated three‐dimensional molecular scaffolds, frameworks of increasing importance in drug discovery and materials science, from readily available starting materials in a single synthetic step. Control experiments and density functional theory calculations elucidated the VL EnT catalysis and olefin‐substitution‐controlled switching between distinct dearomative cycloaddition modes.