Chemodivergent Defluorinative Alkylation and Hydroalkylation of α-Trifluoromethyl Alkenes via Eosin Y Catalysis and EDA Photo-chemistry

Herein, we report a novel, visible-light-induced approach for the selective construction of both gem-difluoroalkenes and trifluoromethyl alkanes from α-trifluoromethyl olefins using alcohol-derived N-alkoxyphthalimides as alkyl radical precursors. This strategy leverages Eosin Y as a photocatalyst in a defluorinative alkylation reaction and a catalyst-free electron donor-acceptor (EDA)-mediated hydroalkyl-ation process. By modulating the reaction conditions, the desired products were selectively obtained with excellent chemo-selectivity and in high yields. The protocol accommodates a wide variety of substrates, including primary, secondary, and tertiary alcohols, as well as diverse α-trifluoromethyl styrenes, and is applicable to late-stage functionalization of natural products and bioactive molecules.