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Mixed Anhydride Intermediates in the Reaction of 5(4H)-Oxazolones with Phosphate Esters and Nucleotides

机译:5(4H)-恶唑酮与磷酸酯和核苷酸反应中的混合酸酐中间体

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摘要

5(4H)-Oxazolones can be formed through the activation of acylated alpha-amino acids or of peptide C termini. They constitute potentially activated intermediates in the abiotic chemistry of peptides that preceded the origin of life or early stages of biology and are capable of yielding mixed carboxylic-phosphoric anhydrides upon reaction with phosphate esters and nucleotides. Here, we present the results of a study aimed at investigating the chemistry that can be built through this interaction. As a matter of fact, the formation of mixed anhydrides with mononucleotides and nucleic acid models is shown to take place at positions involving a mono-substituted phosphate group at the 3'- or 5'-terminus but not at the internal phosphodiester linkages. In addition to the formation of mixed anhydrides, the subsequent intramolecular acyl or phosphoryl transfers taking place at the 3'-terminus are considered to be particularly relevant to the common prebiotic chemistry of alpha-amino acids and nucleotides.
机译:5(4H)-恶唑酮可通过酰化的α-氨基酸或肽C末端的活化而形成。它们构成了生命的起源或生物学早期之前的肽的非生物化学中潜在活化的中间体,并且能够在与磷酸酯和核苷酸反应后产生混合的羧酸-磷酸酐。在这里,我们提出了一项研究结果,旨在研究可以通过这种相互作用建立的化学反应。实际上,显示了具有单核苷酸和核酸模型的混合酸酐的形成发生在涉及3'或5'末端的单取代磷酸基的位置处,而不是在内部磷酸二酯键处。除了形成混合酸酐以外,随后在3'端发生的分子内酰基或磷酰基转移也被认为与α-氨基酸和核苷酸的常见益生元化学特别相关。

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