Selective prebiotic synthesis of phosphoroaminonitriles and aminothioamides in neutral water
Selective prebiotic synthesis of phosphoroaminonitriles and aminothioamides in neutral water
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DOI：
10.1038/s42004-019-0124-5
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发表时间：
2019-02-26
影响因子：
5.9
通讯作者：
Powner, Matthew W.
中科院分区：
文献类型：
--
作者：
Ashe, Kathryn;Fernandez-Garcia, Christian;Powner, Matthew W.
肽在现存生物学中的中心和保守作用表明它们在生命起源中发挥了重要作用。Strecker氨基酸合成似乎是益生元的，但是氨的高pK（aH）（pK（aH）= 9.2）需要高pH反应条件来实现有效的合成，这对益生元氨基酸合成施加了困难的环境限制。在这里，我们证明，diamidophosphate反应有效地与简单的醛和氰化氢在水中，在中性pH值，以提供N-磷氨基腈。N-磷酸氨基腈合成对醛具有高度选择性;酮的转化率很低。N-磷氨基腈与硫化氢在中性pH下反应得到氨基硫代酰胺。高产量（73%-Quant.）的N-磷酸氨基腈在中性pH值，和他们的选择性转化，可能会提供新的见解益生元氨基酸的合成和激活。
The central and conserved role of peptides in extant biology suggests that they played an important role during the origins of life. Strecker amino acid synthesis appears to be prebiotic, but the high pK(aH) of ammonia (pK(aH) = 9.2) necessitates high pH reaction conditions to realise efficient synthesis, which places difficult environmental constraints on prebiotic amino acid synthesis. Here we demonstrate that diamidophosphate reacts efficiently with simple aldehydes and hydrogen cyanide in water at neutral pH to afford N-phosphoro-aminonitriles. N-Phosphoro-aminonitrile synthesis is highly selective for aldehydes; ketones give poor conversion. N-Phosphoro-aminonitriles react with hydrogen sulfide at neutral pH to furnish aminothioamides. The high yield (73%-Quant.) of N-phosphoro-aminonitriles at neutral pH, and their selective transformations, may provide new insights into prebiotic amino acid synthesis and activation.