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Intermolecular dearomative [4 + 2] cycloaddition of naphthalenes via visible-light energy-transfer-catalysis† † Electronic supplementary information (ESI) available: Synthesis, crystallography, computation and characterization details (PDF). CCDC 2173728, 2173729, 2173850, 2173723 and 2190337. For ESI and crystallographic data in CIF or other electronic format see https://doi.org/10.1039/d2sc04005k

ABSTRACT: The dearomative cycloaddition reaction serves as a blueprint for creating sp3-rich three-dimensional molecular topology from flat-aromatic compounds. However, severe reactivity and selectivity issues make this process arduous. Herein, we describe visible-light energy-transfer catalysis for the intermolecular dearomative [4 + 2] cycloaddition reaction of feedstock naphthalene molecules with vinyl benzenes. Tolerating a wide range of functional groups, 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 moderate endo-selectivities. The late-stage modification of the derivatives 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, control experiments, and density-functional theory calculations support energy-transfer catalysis. Constructing 3D molecular scaffolds from aromatic hydrocarbons is challenging. Herein, we report dearomative [4 + 2] cycloaddition reaction of naphthalenes via visible-light EnT catalysis which overcomes issues of unfavorable thermodynamics, low yields, and selectivity.

SUBMITTER: Rai P

PROVIDER: S-EPMC9628934 | biostudies-literature | 2022 Oct

REPOSITORIES: biostudies-literature

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