The peptide formation mediated by cyanate revisited. N-carboxyanhydrides as accessible intermediates in the decomposition of N-carbamoylamino acids.
Similar to many ureas, N-carbamoylamino acids were shown to be hydrolyzed in aqueous solution through elimination mechanisms at close to neutral pH, the nucleophilic attack of water being a minor process. Two competing elimination mechanisms can take place involving either cyanate or isocyanate transient intermediates. Peptide formation was observed and attributed to the latter pathway through the intermediacy of amino acid N-carboxyanhydride (NCA). Eventually, cyanate and its precursors (including urea) unexpectedly behave as amino acid activating agents because of their ability in amino acid carbamoylation. Owing to its ability to generate a background prebiotic production of NCAs on the primitive Earth, this reaction is suggested to have contributed to the origin of life process.
Danger
Grégoire
G
Dynamique des Systèmes Biomoléculaires Complexes, UMR 5073, Université Montpellier 2, CNRS, CC 017, 34095 Montpellier Cedex 5, France.
Boiteau
Laurent
L
Cottet
Hervé
H
Pascal
Robert
R
D000596:Amino Acids / Q000737:chemistry*; D000812:Anhydrides / Q000737:chemistry*; D002219:Carbamates / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry*; D003485:Cyanates / Q000737:chemistry*; D019075:Electrophoresis, Capillary; D008956:Models, Chemical; D010455:Peptides / Q000138:chemical synthesis*; D013997:Time Factors
D000596:Amino Acids; D000812:Anhydrides; D002219:Carbamates; D002264:Carboxylic Acids; D003485:Cyanates; D010455:Peptides