Base‐Induced Hydrophosphination of Acylsilanes at the Carbonyl Carbon Center

Acylsilanes have recently emerged as versatile intermediates in organic synthesis, yet their direct hydrophosphination under mild and sustainable conditions remains underexplored. Herein, we report a base‐mediated (10 mol% NaHMDS) direct hydrophosphination of acylsilanes with various H─P compounds at room temperature within 2 h. This protocol provides rapid and unified access to three major classes of α‐siloxy organophosphorus compounds—phosphonates, phosphinates, and phosphine oxides—which have not been achievable by previous photoinduced carbene insertion or stoichiometric nucleophilic addition–rearrangement strategies. The method features exceptionally broad substrate scope (52 examples, most in >90% yield), including synthetically valuable primary and secondary alkyl acylsilanes that were previously inaccessible. Gram‐scale synthesis and facile derivatizations further demonstrate its practicality.