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 (VLEnT) 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 VLEnT catalysis and olefin-substitution-controlled switching between distinct dearomative cycloaddition modes.