title: Mixed Anhydride Intermediates in the Reaction of 5(4H)-Oxazolones with Phosphate Esters and Nucleotides.
abstract: 5(4H)-Oxazolones can be formed through the activation of acylated α-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 α-amino acids and nucleotides.
authors.affiliation: Institut des Biomolécules Max Mousseron, CNRS, Université de Montpellier, École nationale supérieure de chimie de Montpellier (ENSCM), Place E. Bataillon, 34095, Montpellier Cedex 5, France.
authors.forename: Ziwei
authors.initials: Z
authors.lastname: Liu
authors.affiliation: MRC Laboratory of Molecular Biology, Francis Crick Avenue, Cambridge Biomedical Campus, Cambridge, CB2 0QH, UK.
authors.forename: Lukas
authors.initials: L
authors.lastname: Rigger
authors.affiliation: Institut des Biomolécules Max Mousseron, CNRS, Université de Montpellier, École nationale supérieure de chimie de Montpellier (ENSCM), Place E. Bataillon, 34095, Montpellier Cedex 5, France.
authors.forename: Jean-Christophe
authors.initials: JC
authors.lastname: Rossi
authors.affiliation: MRC Laboratory of Molecular Biology, Francis Crick Avenue, Cambridge Biomedical Campus, Cambridge, CB2 0QH, UK.
authors.forename: John D
authors.initials: JD
authors.lastname: Sutherland
authors.affiliation: Institut des Biomolécules Max Mousseron, CNRS, Université de Montpellier, École nationale supérieure de chimie de Montpellier (ENSCM), Place E. Bataillon, 34095, Montpellier Cedex 5, France. robert.pascal@umontpellier.fr.
authors.forename: Robert
authors.initials: R
authors.lastname: Pascal
mesh_terms: D000812:Anhydrides / Q000737:chemistry; D004952:Esters; D009696:Nucleic Acids / Q000737:chemistry*; D009711:Nucleotides / Q000737:chemistry*; D010081:Oxazolone / Q000737:chemistry*; D010455:Peptides / Q000737:chemistry*; D010710:Phosphates / Q000737:chemistry*
chemical_list: D000812:Anhydrides; D004952:Esters; D009696:Nucleic Acids; D009711:Nucleotides; D010455:Peptides; D010710:Phosphates; C050632:polypeptide C; D010081:Oxazolone
keywords: anhydrides; nucleotides; peptides; phosphates; prebiotic chemistry