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Article Abstract
Visible-light-mediated energy transfer (EnT) photocatalysis has emerged as a highly appealing strategy for converting planar (hetero)arenes into complex, medicinally relevant, three-dimensional (3D) architectures. Current methodologies for intermolecular dearomative photocycloadditions, however, are restricted to bicyclic (hetero)aromatic systems, while the more abundant monocyclic (hetero)arenes remain vastly underexplored. Accessing the triplet state of the ubiquitous monocyclic (hetero)arenes poses a formidable challenge due to their high triplet energy barriers. Herein, we report several EnT-catalyzed intermolecular dearomative cycloadditions of monocyclic heteroarenes with alkenes and bicyclo[1.1.0]butanes. To overcome the intrinsic limitations in triplet-state reactivity and accelerate reaction discovery, we introduced a data-driven three-layer screening strategy that integrates predictive data science tools for mapping excited-state properties with luminescence quenching and reaction-based screening. This synergistic three-layer screening strategy uncovers structure-reactivity relationships between substituted monocyclic heteroarenes and biradical acceptors, facilitating the accelerated discovery of new reactivity. Utilizing this data-driven approach, we developed the EnT-catalyzed intermolecular dearomative cycloaddition of thiophenes, oxazoles, and thiazoles with alkenes/bicyclo[1.1.0]butanes, providing access to unprecedented C(sp)-rich 3D molecular scaffolds.
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