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Cited by 76Origins and Evolution of LifeChemical Reaction MechanismsAdvanced Glycation End Products research

Exploratory Experiments on the Chemistry of the “Glyoxylate Scenario”: Formation of Ketosugars from Dihydroxyfumarate

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Sagi, Vasudeva Naidu, Punna, Venkateshwarlu, Hu, Fang, Meher, Geeta, Krishnamurthy, Ramanarayanan·2012·Journal of the American Chemical Society
DOI 10.1021/ja211383cPMC PMC3284196
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Abstract

In the context of a "glyoxylate scenario" of primordial metabolism, the reactions of dihydroxyfumarate (DHF) with reactive small molecule aldehydes (e.g., glyoxylate, formaldehyde, glycolaldehyde, and glyceraldehyde) in water were investigated and shown to form dihydroxyacetone, tetrulose, and the two pentuloses, with almost quantitative conversion. The practically clean and selective formation of ketoses in these reactions, with no detectable admixture of aldoses, stands in stark contrast to the formose reaction, where a complex mixture of linear and branched aldoses and ketoses are produced. These results suggest that the reaction of DHF with aldehydes could constitute a reasonable pathway for the formation of carbohydrates and allow for alternative potential prebiotic scenarios to the formose reaction to be considered.

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  • This chemistry alternates aldol-type additions of key metabolites (pyruvate, oxaloacetate, malonate) to glyoxylate with the decarboxylation of oxalomalate and oxidative decarboxylations from HKG, malate, oxaloacetate and 3-carboxymalate.

    “This chemistry alternates aldol-type additions of key metabolites (pyruvate, oxaloacetate, malonate) to glyoxylate with the decarboxylation of oxalomalate and oxidative decarboxylations from HKG, malate, oxaloacetate and 3-carboxymalate.116,117”

    From The protometabolic nature of prebiotic chemistry (2023) · cites this paper as [116]

    The ‘Reaction of DHF with Glyoxylate’ section describes condensation of dihydroxyfumarate with glyoxylate followed by decarboxylation of its adducts. It does not describe the claimed additions of pyruvate, oxaloacetate, or malonate, or the specified decarboxylations; searches for oxalomalate, pyruvate, and malonate found no supporting passage. Page numbers were not available in our copy. (LLM, conf=0.76)

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Authors
Sagi, V. N., Punna, V., Hu, F., Meher, G., & Krishnamurthy, R.
Affiliations
Scripps Research Institute (US)
Corresponding author
Krishnamurthy, Ramanarayanan
ORCID
Krishnamurthy, Ramanarayanan
Venue
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Published
2012-02-10
Volume
134
Issue
7
Pages
3577-3589
ISSN
  • 0002-7863 (ISSN-L)
  • 1520-5126
DOI
10.1021/ja211383c
PMC
PMC3284196
OpenAlex
W1986491943
Cited by
76
References
3
Citations by year
2026: 2 · 2025: 2 · 2024: 4 · 2023: 13 · 2022: 5 · 2021: 6 · 2020: 5 · 2019: 7 · 2018: 3 · 2017: 7 · 2016: 5 · 2015: 7 · 2014: 3 · 2013: 3 · 2012: 4
FWCI
2.98
Type
journal article
Language
en
Open access
Licence
Locations
  • Journal of the American Chemical Society (publishedVersion, other-oa)
  • PubMed Central (publishedVersion)
  • PubMed (publishedVersion)
Funders
  • National Science Foundation
  • National Aeronautics and Space Administration
Topics
  • Physical Sciences › Physics and Astronomy › Astronomy and Astrophysics › Origins and Evolution of Life
  • Physical Sciences › Chemistry › Organic Chemistry › Chemical Reaction Mechanisms
  • Life Sciences › Biochemistry, Genetics and Molecular Biology › Clinical Biochemistry › Advanced Glycation End Products research
Keywords
prebiotic chemistry, formose reaction, dihydroxyacetone, aldehydes, glycolaldehyde, glyceraldehyde, formaldehyde, glyoxylic acid
MeSH terms
Aldehydes, Fumarates, Glyoxylates, Ketoses

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