Selective Synthesis\nof Mono- and Bis-Phosphorylated\n(Dihydro)pyrans via TMSCl-Mediated Cascade Phosphorylation Cycloisomerization\nof Enynones

A chlorotrimethylsilane\n(TMSCl)-mediated cascade phosphorylation\nand cycloisomerization of enynones with diphenylphosphine oxides is\npresented. This methodology enables the highly selective synthesis\nof monophosphorylated 2<i>H</i>-pyrans and bisphosphorylated\ndihydropyrans through precise solvent-reagent stoichiometry control.\nThe strategy demonstrated excellent functional group compatibility\nand high yields (up to 96%), providing facile access to structurally\ndiverse phosphorylated heterocycles with potential applications in\nmedicinal chemistry and materials science.