Photoinduced Electron Donor–Acceptor Complex-Mediated Aminomethylation of <i>gem</i> -Difluoroalkenes: Synthesis of Various β,β-Difluoroamines

-hydroxyphthalimide (NHPI) esters. This method facilitates the efficient synthesis of diverse β,β-difluoroamines under mild conditions, demonstrating a broad substrate scope with excellent functional group compatibility. Systematic mechanistic studies elucidate a photocatalyst-enhanced EDA-enabled radical pathway. Significantly, the synthetic utility of this strategy is further exemplified by its successful extension to hydroxyl- and thiol-methylation reactions, delivering a range of β,β-difluoroalcohol and β,β-difluorothiol derivatives in high yields.