Prebiotic synthesis of simple sugars by photoredox systems chemistry

• Published in: Nature chemistry Vol. 4; no. 11; pp. 895 - 899
• Main Authors: Ritson, Dougal, Sutherland, John D.
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 01-11-2012; Nature Publishing Group
• Subjects: 639/638/439; 639/638/45; 639/638/549; Analytical Chemistry; Biochemistry; Carbohydrates - chemical synthesis; Carbohydrates - chemistry; Carbon; Chemistry; Chemistry Techniques, Synthetic; Chemistry/Food Science; Copper; Hydrogen; Hydrogen Cyanide - chemistry; Inorganic Chemistry; Irradiation; Organic Chemistry; Oxidation-Reduction; Photochemical Processes; Physical Chemistry; Prebiotics; Raw materials; Sugar
• ISSN: 1755-4330; 1755-4349
• DOI: 10.1038/nchem.1467

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.
A demonstration of simple sugar synthesis from single carbon feedstocks would provide significant support for the involvement of RNA in the origin of life. Here, hydrogen cyanide is shown to feed a cyanocuprate photoredox cycle that ultimately provides both the starting material and the reducing power necessary for a Killiani–Fischer-type sugar synthesis.