<i>Cis</i> -difluoromethyl hetarylative dearomatization by a radical docking-migration cascade

Despite the significant advances in dearomatization reactions, the challenge of achieving uncyclized dearomatization to produce thermodynamically unstable 1,2-<i>cis</i>-products remains unresolved. Here, we present a novel approach for uncyclized <i>cis</i>-selective dearomatization reaction <i>via</i> a radical docking-migration cascade. The reaction proceeds under mild photochemical conditions, simultaneously incorporating a CF₂H and a hetaryl group into indoline backbones. A wide range of indoles with diverse functional groups are compatible with the reaction. Furthermore, this method is also suitable for the dearomatization of benzothiophenes, furans, thiophenes and a few polycyclic aromatic hydrocarbons. This protocol features excellent selectivities, broad product diversity, and does not require photosensitizers. DFT calculations rationalize the observed regioselectivities for various heteroarenes and <i>cis</i>-stereoselectivities.