Prebiotic synthesis of simple sugars by photoredox systems chemistry

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Abstract

A recent synthesis of activated pyrimidine ribonucleotides under prebiotically plausible conditions relied on mixed oxygenous and nitrogenous systems chemistry. As it stands, this synthesis provides support for the involvement of RNA in the origin of life, but such support would be considerably strengthened if the sugar building blocks for the synthesis—glycolaldehyde and glyceraldehyde—could be shown to derive from one carbon feedstock molecules using similarly mixed oxygenous and nitrogenous systems chemistry. Here, we show that these sugars can be formed from hydrogen cyanide by ultraviolet irradiation in the presence of cyanometallates in a remarkable systems chemistry process. Using copper cyanide complexes, the process operates catalytically to disproportionate hydrogen cyanide, first generating the sugars and then sequestering them as simple derivatives.

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Figure 1: Homologation routes to simple sugars from formaldehyde 1.
Figure 2: Photoredox cycling of copper cyanide complexes in the presence of hydrogen cyanide 5.
Figure 3: 13C-NMR analysis of the organic intermediates and products formed by the photoredox cycling of copper cyanide complexes in the presence of hydrogen cyanide 5.
Figure 4: 1H-NMR analysis of photochemical products.
Figure 5: Disproportionation of hydrogen cyanide 5 and ensuing systems chemistry.

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Acknowledgements

This work was funded by the Engineering and Physical Sciences Research Council through the provision of a postdoctoral fellowship (to D.R.) and by the Medical Research Council (project no. MC_UP_A024_1009). The authors thank S. Freund and T. Rutherford for assistance with NMR spectroscopy.

Author information

J.D.S. and D.R. conceived and designed the experiments. D.R. performed the experiments. J.D.S. and D.R. analysed the data and co-wrote the paper.

Correspondence to John D. Sutherland.

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The authors declare no competing financial interests.

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Ritson, D., Sutherland, J. Prebiotic synthesis of simple sugars by photoredox systems chemistry. Nature Chem 4, 895–899 (2012) doi:10.1038/nchem.1467

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