This work was funded by the Medical Research Council (project no. MC_UP_A024_1009), the Engineering and Physical Sciences Research Council, and by the Origins of Life Challenge; we thank Harry Lonsdale for the latter. Thanks also to Willie Motherwell for bringing certain key references to our attention.
Synthesis of Aldehydic Ribonucleotide and Amino Acid Precursors by Photoredox Chemistry†
Version of Record online: 22 APR 2013
© 2013 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
Angewandte Chemie International Edition
Volume 52, Issue 22, pages 5845–5847, May 27, 2013
How to Cite
Ritson, D. J. and Sutherland, J. D. (2013), Synthesis of Aldehydic Ribonucleotide and Amino Acid Precursors by Photoredox Chemistry. Angew. Chem. Int. Ed., 52: 5845–5847. doi: 10.1002/anie.201300321
- Issue online: 17 MAY 2013
- Version of Record online: 22 APR 2013
- Manuscript Revised: 23 MAR 2013
- Manuscript Received: 14 JAN 2013
- Funded Access
- Medical Research Council. Grant Number: MC_UP_A024_1009
- Engineering and Physical Sciences Research Council
- Origins of Life Challenge
- 5After 6 h irradiation, the system had simplified, and acetaldehyde 12 and formaldehyde 4 were the predominant products. The apparent yield of 12 at this point was 15 % (as measured by 1H NMR integration relative to an added standard of pentaerythritol) based on starting glycolonitrile 5. The production of 4 also consumes 5 but the amount of 4 could not be quantitated by integration owing to overlap with the HOD signal. We did not quantitate products by another method because the system generates multiple biomolecule precursors, so the yield of any particular product has less significance than it does in conventional synthetic chemistry, it being unclear what the ideal product distribution should be: the compositional ratio of 5/6/11/12 changes from 14:41:8:37 after 2 h to 0:15:10:75 after 4 h, and 0:0:12:88 after 6 h.
- 6In our previous work using hydrogen cyanide 1 as substrate and reductant, cyanate was formed by hydrolysis of cyanogen. By analogy therefore, it is possible that in this work, thiocyanate 13 is formed by (copper-catalyzed) thiolysis of cyanogen. Alternatively, 13 could result from the nucleophilic attack of cyanide ion on the terminal sulfur atom of an oligosulfide formed by oxidation of H2S 10.
- 7Known in conventional synthetic chemistry for example: Tetrahedron 1964, 20, 357–372; J. Chem. Soc. 1954, 3045–3051. The potential utility of such deoxygenation in the prebiotic chemistry of hydrogen cyanide derivatives has been emphasized by Eschenmoser: Chem. Biodiversity 2007, 4, 554–573., , , , , , ,
- 11Russ. J. Inorg. Chem. 1962, 7, 640–643.,
- 12Chem. Ztg. 1922, 46, 661; , Russ. J. Inorg. Chem. 1962, 7, 1187–1189.,