Prebiotic access to enantioenriched amino acids via peptide- mediated transamination reactions

• 成果类型: Article
• 署名作者: Yu, Jinhan; Daru, Andrea; Deng, Min; Blackmond, Donna G.
• 署名单位: University of Chicago; Scripps Research Institute
• 刊物名称: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
• ISSN/ISSBN: 0027-13988
• DOI: 10.1073/pnas.2315447121
• 发表日期: 2024-02-13
• 关键词: asymmetric-synthesis; nonenzymatic transamination; metal-complexes; ketonic acids; stereoselectivity; precursors; origin; rna

摘要

The kinetic resolution of racemic amino acids mediated by dipeptides and pyridoxal provides a prebiotically plausible route to enantioenriched proteinogenic amino acids. The enzymatic transamination cycles that are key to modern biochemical formation of enantiopure amino acids may have evolved from this half of the reversible reaction couple. Kinetic resolution of racemic precursors emerges as a general route to enantioenrichment under prebiotic conditions. Significance While much progress has been made in developing prebiotically plausible synthetic chemical routes to RNA, DNA, and peptides, as well as in prebiotic metabolic pathways, the question of the emergence of biological homochirality has often been left unexplored. Our work suggests that modern biological transamination may have evolved from a prebiotic half- reaction in reverse, effecting a kinetic resolution of racemic amino acids that preferentially leaves behind the proteinogenic amino acid enantiomer. This reaction joins several other recently reported prebiotically plausible kinetic resolutions that have been shown to produce enantioenriched sugar and amino acid building blocks. Kinetic resolution may be seen as an effective means of imparting stereochemical control that preceded and aided the development of highly selective asymmetric biocatalysts.