Six-membered cyclic phosphates (2-phenoxy-2-oxo-1, 3, 2-dioxaphosphorinanes) bearing an internal protected or unprotected hydroxyl group were designed, synthesized, and studied by NMR and computational methods. Selective opening of O-isopropylidene- protected 1, 2-diols at the primary site was achieved with either triethylsilane or trimethylallylsilane in the presence of BF3⊙ OEt2. Applied to 5, 6-O- ...