Access to All-Carbon Quaternary Centers by Photocatalytic Fluoroalkylation of α‑Halo Carbonyl Compounds

Perfluoroalkyl groups have become significantly important in pharmaceutical and agrochemical applications. In this study, we present a visible light-mediated photoredox neutral strategy for the fluoroalkylation of tertiary alkyl chlorides under transition-metal-free conditions. This method allows for the facile synthesis of fluoroalkylated all-carbon quaternary centers, exhibiting excellent functional group compatibility. Mechanistic studies reveal the involvement of two reactive radical intermediates and the in situ formation of metal enolates in a radical-polar crossover manner. The versatility of this methodology is demonstrated through synthetic transformations based on the carbonyl group, showcasing its potential for the rapid assembly of diverse organic molecules bearing fluoroalkyl all-carbon quaternary centers.