HP(O)Ph ₂ -Mediated Hydrodefluorination of Polyfluoro(hetero)arenes

High Resolution Image Download MS PowerPoint Slide The roles of H-phosphoryl compounds [HP(O)R′R″] in various transformations remain insufficiently elucidated, particularly concerning their contributions to facilitating the conversion of inert chemical bonds. Herein, we report a highly selective hydrodefluorination (HDF) reaction of polyfluoro(hetero)aromatic compounds mediated by HP(O)Ph 2, which does not require complex constrained phosphorus architectures or external reducing agents. Notably, H-phosphoryl compounds, especially the commercially available, bench-stable, and inexpensive HP(O)Ph 2 used in this study, were discovered for the first time to function as both a defluorinative surrogate and an H-reagent, displaying unconventional HDF reactivity with the assistance of water. By employing this protocol, a variety of partially fluorinated (hetero)aromatic scaffolds can be synthesized. Furthermore, the approach demonstrates excellent regioselectivity, enables postfunctionalization of complex molecules, and allows for the transformation of the resulting products into other value-added organofluorides, highlighting its potential in medicinal and organic chemistry.