Evidence for tunneling in base-catalyzed isomerization of glyceraldehyde to dihydroxyacetone by hydride shift under formose conditions Article Swipe
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· 2015
· Open Access
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· DOI: https://doi.org/10.1073/pnas.1503739112
· OA: W2020242732
Significance This paper describes experimental and computational evidence that the hydride shift that converts glyceraldehyde to dihydroxyacetone at basic pH with Ca 2+ catalysis proceeds primarily by quantum tunneling. This answers the last question about the mechanism of the formose reaction, in which formaldehyde is converted to higher sugars under these conditions. This reaction has long been seen as an important clue to the formation of molecules needed for life under prebiotic conditions on Earth. Earlier work showed that the mechanism involved a hydride shift, not a deprotonation, and this work confirms those conclusions. It shows the critical role of tunneling, a quantum effect important in chemistry and biology, and in likely prebiotic reactions on Earth or elsewhere, one concern of astrobiology.