Ternary Photoredox/Nickel/Halide Catalysis for the Phosphorylation of Alcohols with White Phosphorus

Dialkyl phosphites (DAPIs) are important precursors in the formation of phosphorus–carbon and phosphorus–heteroatom bonds with significant industrial applications. Traditional PCl3-based procedures suffer from high waste production and toxic reaction conditions. The direct conversion of white phosphorus (P4) to DAPIs can circumvent these issues by avoiding the use of Cl2 and PCl3. We present a waste-free, environmentally friendly approach for synthesizing DAPIs using P4 and alcohols, leveraging a combination of photoredox catalyst, nickel catalyst, and halide anion. This photocatalytic method enables the efficient coupling of various alcohols. Advantageously, this method is also suitable for the synthesis of trialkyl phosphates and triaryl phosphorotrithioates.