Catalytic Activation of Bis(2,2,2‐trifluoroethyl) Phosphite with Hf(IV) for the Synthesis of Mixed Dialkyl Phosphites

We developed a second generation of Lewis acid catalyst enabling selective and user‐friendly phosphonylation of diverse alcohols. This one‐pot method utilizes P(III) reagent bis(2,2,2–trifluoroethyl) phosphite under mild conditions. Exploring the influence of metal selection in Lewis acid catalysts revealed four highly active complexes for alcohol phosphonylation: Zn(II), Al(III), Zr(IV), and Hf(IV). Notably, Hf(IV) displayed superior selectivity compared to the previously developed Zn(II) catalyst.