The gas phase aldose-ketone isomerization mechanism: Direct interconversion of the model hydroxycarbonyls 2-hydroxypropanal and hydroxyacetone

Abstract

We report a novel mechanism for the interconversion of 2-hydroxypropanal with its more-stable ketone isomer hydroxyacetone. Reaction proceeds via concerted transfer of two H atoms, requires a barrier of only ∼40 kcal mol−1, bypasses the enediol intermediate, and is general for α-hydroxy carbonyls. A similar isomerization mechanism is shown to persist for β, γ, and δ-hydroxy carbonyls; these compounds are skeletal forms of the monosaccharides and this work, therefore, discloses the gas-phase mechanism for aldose-ketose isomerization. As an example, the isomerization of glyceraldehyde to dihydroxyacetone is shown to proceed via this mechanism with a barrier of 31 kcal mol−1. Rate coefficients ..