1,3-Dioxolane-4-ol Hemiacetal Stores Formaldehyde and Glycolaldhyde in the Gas Phase
André K. Eckhardt, Raffael C. Wende and Peter R. Schreiner
J. Am. Chem. Soc. 2018, 140,12333–12336. . Highlight: Cover picture of this issue.
We report the spontaneous gas-phase formation of 1,3-dioxolane-4-ol, a mixed hemiacetal resulting from the addition of glycolaldehyde to formaldehyde. It was spectroscopically characterized by matching matrix IR spectra with coupled cluster computations. The formation of the hemiacetal must be surface-catalyzed owing to the very high computed reaction barrier of 39.8 kcal mol–1. The reaction barrier is lowered by almost 20 kcal mol–1 when a single water molecule acts as a proton shuttle in a favorable six-membered transition state. We characterized the hemiacetal in solution via NMR spectroscopy and followed its decomposition into its constituents within a few hours; it also dissociates upon contact with water. Sugars form in the presence of Ca(OH)2, in line with formose-type reactivity. 1,3-Dioxolane-4-ol may be considered a storage form for formaldehyde and glycolaldehyde that is rather stable in the gas-phase.