Direct deoxygenative arylation of saccharides via phosphorus-assisted C−OH bond activation

is developed for initiating the key β-scission step. Importantly, the glycosyl donors are bench-stable and readily available, addressing the issues associated with previous donors. Furthermore, this method offers an attractive strategy for the direct synthesis of drug-sugar conjugates and therapeutic agents. Mechanistic experiments and density functional theory (DFT) calculations provide strong support for the proposed reaction mechanism.