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

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Title: The gas phase aldose-ketone isomerization mechanism: Direct interconversion of the model hydroxycarbonyls 2-hydroxypropanal and hydroxyacetone.
Authors: Sun, Jing1, So, Sui1, da Silva, Gabriel1 gdasilva@unimelb.edu.au
Source: International Journal of Quantum Chemistry. 10/15/2017, Vol. 117 Issue 20, pn/a-N.PAG. 5p.
Subjects: Hydroxypropanone, Hydroxycarbonyls, Gas phase reactions, Isomerization, Aldoses, Ketones
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 and thermochemical properties are reported for the isomerization of 2-hydroxypropanal and hydroxyacetone for use in detailed kinetic models. Additionally, RRKM theory k( E) values for this reaction suggest that it may transpire in the troposphere following solar excitation. [ABSTRACT FROM AUTHOR]
Copyright of International Journal of Quantum Chemistry is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Data: The gas phase aldose-ketone isomerization mechanism: Direct interconversion of the model hydroxycarbonyls 2-hydroxypropanal and hydroxyacetone.
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  Data: <searchLink fieldCode="AR" term="%22Sun%2C+Jing%22">Sun, Jing</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22So%2C+Sui%22">So, Sui</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22da+Silva%2C+Gabriel%22">da Silva, Gabriel</searchLink><relatesTo>1</relatesTo><i> gdasilva@unimelb.edu.au</i>
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  Data: <searchLink fieldCode="JN" term="%22International+Journal+of+Quantum+Chemistry%22">International Journal of Quantum Chemistry</searchLink>. 10/15/2017, Vol. 117 Issue 20, pn/a-N.PAG. 5p.
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  Data: <searchLink fieldCode="DE" term="%22Hydroxypropanone%22">Hydroxypropanone</searchLink><br /><searchLink fieldCode="DE" term="%22Hydroxycarbonyls%22">Hydroxycarbonyls</searchLink><br /><searchLink fieldCode="DE" term="%22Gas+phase+reactions%22">Gas phase reactions</searchLink><br /><searchLink fieldCode="DE" term="%22Isomerization%22">Isomerization</searchLink><br /><searchLink fieldCode="DE" term="%22Aldoses%22">Aldoses</searchLink><br /><searchLink fieldCode="DE" term="%22Ketones%22">Ketones</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: 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 and thermochemical properties are reported for the isomerization of 2-hydroxypropanal and hydroxyacetone for use in detailed kinetic models. Additionally, RRKM theory k( E) values for this reaction suggest that it may transpire in the troposphere following solar excitation. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of International Journal of Quantum Chemistry is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.1002/qua.25434
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      – Code: eng
        Text: English
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      – SubjectFull: Hydroxypropanone
        Type: general
      – SubjectFull: Hydroxycarbonyls
        Type: general
      – SubjectFull: Gas phase reactions
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      – SubjectFull: Isomerization
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      – SubjectFull: Aldoses
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      – TitleFull: The gas phase aldose-ketone isomerization mechanism: Direct interconversion of the model hydroxycarbonyls 2-hydroxypropanal and hydroxyacetone.
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              Text: 10/15/2017
              Type: published
              Y: 2017
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