2-Azaallyl Anions as Light-Tunable Super-Electron-Donors: Coupling with Aryl Fluorides, Chlorides, and Bromides

Herein, we present 2-azaallyl anions as colored super-electron-donors capable of reducing a collection of aryl halides via a single electron transfer and coupling with the corresponding radicals to forge new C C bonds. This offers a robust approach for the arylation of 2-azaallyls. Mechanistic studies demonstrate that the reactions proceed via either a radical pathway for aryl bromides and chlorides or a SNAr mechanism for activated aryl fluorides. Moreover, we demonstrate that irradiation of the colored 2-azaallyl anions with visible light can further extend their reducing power, enabling radical-mediated coupling with otherwise unreactive electron-rich aryl halides. Isolated yields up to 94% are obtained and the overall relevance and utility is demonstrated by the derivatization of both a known pharmaceutical agent and a popular fluorophore.