SnCl2‐Catalyzed Phosphorylation of Alcohols and Selective Phosphorylation/Phosphinoylation of Carbohydrates

Phosphorylated molecules, particularly phosphorylated carbohydrates, have garnered significant interest due to their distinct biological activities, driving an urgent demand for efficient phosphorylation strategies. In this study, we demonstrate the successful development of a SnCl2‐catalyzed protocol for the phosphorylation of alcohols and carbohydrates. Notably, the reaction efficiency was found to be critically dependent on the addition order of SnCl2 and N,N‐diisopropylethylamine, a phenomenon systematically investigated through mechanistic studies. A one‐pot sequential ketalization/phosphorylation strategy was established for polyol substrates, enabling streamlined access to phosphorylated derivatives. The versatility of this approach was further exemplified by achieving selective phosphorylation/phosphinoylation of carbohydrates.