Intermolecular Dearomative [4+2] Cycloaddition of Naphthalenes via Visible-Light Energy-Transfer-Catalysis

Dearomative cycloaddition reaction serves as a blueprint for creating three-dimensional molecular topology from flat-aromatic compounds. However, severe reactivity and selectivity issues make this process challenging. Herein, we describe visible-light energy-transfer catalysis for the intermolecular dearomative [4+2] cycloaddition reaction of feed-stock naphthalene molecules with vinyl benzenes. Tolerating a wide range of functional groups, a variety of structurally diverse 2-acyl naphthalenes and styrenes could easily be converted to a diverse range of bicyclo[2.2.2]octa-2,5-diene scaffolds in high yields and selectivities. The late-stage modification of pharmaceutical agents further demonstrated the broad potentiality of this methodology. The efficacy of the introduced methods was further highlighted by the post-synthetic diversification of the products. Furthermore, photoluminescence, electrochemical, kinetic, and control experiments support the energy transfer catalysis