HP(O)Ph2‑Mediated Hydrodefluorination of Polyfluoro(hetero)arenes.

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)-Ph2, 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)-Ph2 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.