N-Carbamoyl-α-Amino Acids Rather than Free α-Amino Acids Formation in the Primitive Hydrosphere: A Novel Proposal for the Emergence of Prebiotic Peptides

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Abstract
Our previous kinetic and thermodynamic studies upon the reactional system HCHO/HCN/ NH3 in aqueous solutions are completed. In the assumed prebiotic conditions of the primitive earth ([HCHO] and [HCN] near 1 g L−1, T = 25 °C, pH = 8, [NH3] very low), this system leads to 99.9% of α-hydroxyacetonitrile and 0.1% of α-aminoacetonitrile (precursor of the α-amino acid). The classical base-catalyzed hydration of nitriles, slow and not selective, can not modify significantly this proportion. On the contrary, we found two specific and efficient reactions of α-aminonitriles which shift the initial equilibrium in favor of the α-aminonitrile pathway. The first reaction catalyzed by formaldehyde generates α-aminoamides, precursors of α-aminoacids. The second reaction catalyzed by carbon dioxide affords hydantoins, precursors of N-carbamoyl-α-aminoacids. In the primitive hydrosphere, where the concentration in carbon dioxide was estimated to be higher than that of formaldehyde, the formation of hydantoins was consequently more efficient. The rates of hydrolysis of the α-aminoacetamide and of the hydantoin at pH 8 being very similar, the synthesis of the N-carbamoyl-α-amino acid seems then to be the fatal issue of the HCHO/HCN/NH3 system that nature used to perform its evolution. These N-protected α-amino acids offer new perspectives in prebiotic chemistry, in particular for the emergence of peptides on the prebiotic earth.