The gas phase aldose-ketone isomerization mechanism: Direct interconversion of the model hydroxycarbonyls 2-hydroxypropanal and hydroxyacetone
Jing Sun, Sui So, Gabriel da Silva
International Journal of Quantum Chemistry | WILEY | Published : 2017
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 ..View full abstract
Related Projects (2)
Awarded by Australian Research Council (ARC)
This work was supported by the Australian Research Council (ARC) through the Discovery Projects (DP110103889) and Future Fellowship (FT130101304) schemes.