Easy Access to Derivatives of 2-(Hydroxymethyl)propane-1,2,3-triol (Isoerythritol) with up to Four Separately Addressable Functionalities

5-Methylene-2-oxo[1,3,2]dioxathiane (2) was obtained in 91% yield from 2-methylenepropane-1,3-diol (1) and thionyl chloride. The cyclic sulfite 2 reacts with a variety of nucleophiles to give formally monosubstituted products 3 of the diol 1 in 62−77% yield. Oxidation of 2 with RuCl3/NaIO4 yields the diprotected tetraol 5-(hydroxymethyl)-2,2-dioxo[1,3,2]dioxathian-5-ol (7) in 86% yield, which can be used to easily access tetrafunctional derivatives of 2-(hydroxymethyl)propane-1,2,3-triol (isoerythritol); for example, acetylation with acetic anhydride furnishes in 96% yield the primary acetate 11, which reacts with potassium cyanide and sodium azide to give the 2-cyano- and 2-(azidomethyl)propane-1,2,3-triol monoacetates 12a,b (78 and 82% yield, respectively). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)