Reversing the Chemoselectivity in Photocatalytic C–F Bond Cleavage Enabled by Zirconocene and Photoredox Catalysis

The development of chemoselective defluorination reactions is highly desirable due to the exceptional stability of the C–F bond compared to other functional groups. Recent advances in photocatalysis have enabled cataytic single-electron transfer (SET) processes, offering an alternative to stoichiometric methods that rely on strong reducing agents. However, these strategies have primarily focused on trifluoromethyl substrates, with limited success for compounds containing fewer fluorine atoms, which are inherently more resistant to SET. Herein, we report a novel defluorination strategy for α-fluorocarbonyl compounds, employing zirconocene and photoredox catalysis. Our method leverages the strong fluorine affinity of zirconocene and bypassed reliance on reduction potential, focusing instead on the bond dissociation energy of the fluorinated molecules. This methodology offers a complementary ap-proach for catalytic C–F bond cleavage under visible-light conditions.