An Efficient and Unambiguous Synthesis of 2-Hydroxymethyl-1, 3-Propanediol

Abstract
In 1949, Fujui3 reported the synthesis of what was presumed to be 2-hydroxymethyl-1, 3-propanediol (4) in 70% yield by the condensation of acetaldehyde with formaldehyde (1:2.5 molar ratio) in the presence of calcium hydroxide, and subsequent catalytic hydrogenation over a nickel catalyst. The product was reported to have a melting point of 182°. In 1955, the triester tris-(carbethoxy) methane (5) was reduced with lithium aluminum hydride to give a product with a reported melting point of 58–62°; the yield was only 5%.4 Owing to the conflicting data in the literature and the vast potential of 4; we have developed an efficient and unambiguous route to 4; this scheme is also adaptable to clean conversions to mono-, di- and tri-O-substituted derivatives of 4: