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Nonenzymatic formation of “energy-rich” lactoyl and glyceroyl thioesters from glyceraldehyde and a thiol

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The “energy-rich” thioester, N-acetyl-S-lactoylcysteine, is formed under anaerobic conditions from glyceraldehyde and N-acetylcysteine at ammbient temperature in aqueous solutions of sodium phosphate (pH 7.0). The conversion of glyceraldehyde to lactoyl thioester occurs at a rate of about 0.4%/day in reactions with 10 mM glyceraldehyde, 10 mM thiol, and 500 mM sodium phosphate (pH 7.0). Thioester formation proceeds at an estimated efficiency of 76%, since a similar reaction with 12.5 mM thiol yields 50.7% lactate at 6 months from only 66.5% of the glyceraldehyde (or its isomer, dihydroxyacetone). The formation of lactoyl thioester most likely occurs by the phosphate-catalyzed dehydration of glyceraldehyde to give pyruvaldehyde, which combines with thiol to form a hemithioacetal that rearranges to the thioester. A second energyrich thioester, N-acetyl-S-glyceroylcysteine, is also produced from glyceraldehyde when these reactions are carried out in the presence of oxygen and to a limited extent in the absence of oxygen. In the presence of oxygen the formation of glyceroyl thioester continues until the thiol disappears completely by oxidation. The significance of these reactions to the energetics of the origin of life is discussed.

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tert-butyldimethylsilyl group


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Weber, A.L. Nonenzymatic formation of “energy-rich” lactoyl and glyceroyl thioesters from glyceraldehyde and a thiol. J Mol Evol 20, 157–166 (1984). https://doi.org/10.1007/BF02257376

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Key words

  • Glyceraldehyde
  • Intramolecular rearrangement
  • Oxidation
  • Lactoyl thioester
  • Glyceroyl thioester
  • Prebiotic