{"title":"Prebiotic thiol-catalyzed thioamide bond formation","authors":"Andrew S. Hyde, Christopher H. House","doi":"10.1186/s12932-024-00088-6","DOIUrl":null,"url":null,"abstract":"<div><p>Thioamide bonds are important intermediates in prebiotic chemistry. In cyanosulfidic prebiotic chemistry, they serve as crucial intermediates in the pathways that lead to the formation of many important biomolecules (e.g., amino acids). They can also serve as purine and pyrimidine precursors, the two classes of heterocycle employed in genetic molecules. Despite their importance, the formation of thioamide bonds from nitriles under prebiotic conditions has required large excesses of sulfide or compounds with unknown prebiotic sources. Here, we describe the thiol-catalyzed formation of thioamide bonds from nitriles. We show that the formation of the simplest of these compounds, thioformamide, forms readily in spark-discharge experiments from hydrogen cyanide, sulfide, and a methanethiol catalyst, suggesting potential accumulation on early Earth. Lastly, we demonstrate that thioformamide has a Gibbs energy of hydrolysis (<span>\\(\\Delta G^{\\circ }_r\\)</span>) comparable to other energy-currencies on early Earth such as pyrophosphate and thioester bonds. Overall, our findings imply that thioamides might have been abundant on early Earth and served a variety of functions during chemical evolution.</p></div>","PeriodicalId":12694,"journal":{"name":"Geochemical Transactions","volume":"25 1","pages":""},"PeriodicalIF":0.9000,"publicationDate":"2024-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11299287/pdf/","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Geochemical Transactions","FirstCategoryId":"89","ListUrlMain":"https://link.springer.com/article/10.1186/s12932-024-00088-6","RegionNum":4,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"GEOCHEMISTRY & GEOPHYSICS","Score":null,"Total":0}
引用次数: 0
Abstract
Thioamide bonds are important intermediates in prebiotic chemistry. In cyanosulfidic prebiotic chemistry, they serve as crucial intermediates in the pathways that lead to the formation of many important biomolecules (e.g., amino acids). They can also serve as purine and pyrimidine precursors, the two classes of heterocycle employed in genetic molecules. Despite their importance, the formation of thioamide bonds from nitriles under prebiotic conditions has required large excesses of sulfide or compounds with unknown prebiotic sources. Here, we describe the thiol-catalyzed formation of thioamide bonds from nitriles. We show that the formation of the simplest of these compounds, thioformamide, forms readily in spark-discharge experiments from hydrogen cyanide, sulfide, and a methanethiol catalyst, suggesting potential accumulation on early Earth. Lastly, we demonstrate that thioformamide has a Gibbs energy of hydrolysis (\(\Delta G^{\circ }_r\)) comparable to other energy-currencies on early Earth such as pyrophosphate and thioester bonds. Overall, our findings imply that thioamides might have been abundant on early Earth and served a variety of functions during chemical evolution.
硫酰胺键是生物前化学的重要中间体。在氰硫代前生物化学中,硫酰胺键是许多重要生物大分子(如氨基酸)形成过程中的关键中间体。它们还可以作为嘌呤和嘧啶的前体,即基因分子中使用的两类杂环。尽管硫代酰胺键非常重要,但在生前条件下从腈中形成硫代酰胺键需要大量过量的硫化物或生前来源不明的化合物。在这里,我们描述了硫醇催化下由腈形成硫代酰胺键的过程。我们表明,在火花放电实验中,氰化氢、硫化物和甲硫醇催化剂很容易形成这些化合物中最简单的硫代甲酰胺,这表明硫代甲酰胺可能在早期地球上积累。最后,我们证明硫代甲酰胺的水解吉布斯能(Δ G r ∘)与早期地球上的其他能量货币(如焦磷酸和硫酯键)相当。总之,我们的研究结果表明,硫代酰胺在早期地球上可能非常丰富,并在化学进化过程中发挥着多种功能。
期刊介绍:
Geochemical Transactions publishes high-quality research in all areas of chemistry as it relates to materials and processes occurring in terrestrial and extraterrestrial systems.