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The addition-cyclocondensation reactions of three β-hydroxyketones with four dialkyl phosphites gave 2-alkoxy-3-hydroxy-1,2-oxaphospholane-2-oxides ("α-hydroxyphostones") (7), in moderate yields. In the solid state and in solution, these compounds exist as dimers with hydrogen bonding between the hydroxyl group and the phosphoryl oxygen atom of an adjacent molecule. The crystal and molecular structure of 3-hydroxy-2-methoxy-3,5,5-trimethyl-1,2-oxaphospholane-2-oxide (7 a) has been determined bydoi:10.1515/znb-1983-0914 fatcat:lwxdamp4fbbvpgogwbrcxlhcqu