Difluoroenol Phosphinates as Versatile Difluoroenolate Surrogates: Synthesis and Applications in Defluorination and Deoxygenative Coupling

We report defluorinative and deoxygenative functionalization reactions of trifluoromethyl ketones mediated by the phospha-Brook rearrangement, offering a streamlined approach to selectively modifying fluorinated compounds. Trifluoromethyl ke-tones react with phosphine oxides to undergo a phospha-Brook rearrangement followed by β-fluoride elimination, providing difluoromethyl ketones in good yields. By tuning the reaction conditions, we achieved the selective one-pot synthesis of monofluoromethyl ketones and methyl ketones, demonstrating the method’s versatility across a range of fluorine-containing derivatives. Furthermore, we successfully demonstrated a range of deoxygenative transformations of key intermediates, such as difluoroenol phosphinates, showcasing their potential as versatile building blocks for diverse functionalizations. These findings not only expand the synthetic toolbox for fluorine-containing molecules but also highlight the utility of phospho-nate intermediates in developing novel reaction pathways.