N-Carbamoyl Amino Acid Solid–Gas Nitrosation by NO/NO x : A New Route to Oligopeptides via α-Amino Acid N-Carboxyanhydride. Prebiotic Implications

Abstract

Alpha-N-Carbamoyl amino acid (CAA), whose conditions of formation in a prebiotic hydrosphere have been described previously (Taillades et al. 1998), could have been an important intermediate in prebiotic peptide synthesis through reaction with atmospheric NOx. Nitrosation of solid CAA (glycine or valine derivative) by a 4/1 NO/O2 gaseous mixture (1 atm) yields N-carboxyanhydride (NCA) quantitatively in less than 1 h at room temperature. The crude solid NCA undergoes quantitative oligomerization (from trimer to nonamer under the conditions we used) when treated with a (bi)carbonate aqueous buffer at pH 9. We therefore suggest that part of the prebiotic amino acid activation/polymerization process may have taken place in a dry phase ("drying-lagoon" scenario).

From Interstellar Amino Acids to Prebiotic Catalytic Peptides: A Review

“…N-Carbamoyl amino acids have been shown to be very interesting precursors of Ncarboxyanhydrides [52] [53]. N-Phosphoryl a-amino acids lead to oligopeptides via a five-membered cyclic pentacoordinate phosphoric-carboxylic mixed anhydrides resembling the N-carboxyanhydrides [54].…”

The Production ofde novo Folded Proteins by a Stepwise Chain Elongation: A Model for Prebiotic Chemical Evolution of Macromolecular Sequences

“…Condensation of N-carboxy anhydrides (NCA), conversely, begins to be accepted as a prebiotic method of chain formation [10], and, in fact, the group of Commeyras has approached the very problem of the prebiotic formation of sequential peptides by this method [10 -12] (see also Blocher et al [13]). However, also in this case, the critical question of the production of multiple identical copies of long (30 or more) cooligopeptides could not yet be achieved.…”

An Expeditious Multigram‐Scale Synthesis of Lysine Dendrigraft (DGL) Polymers by Aqueous N‐Carboxyanhydride Polycondensation

“…Synthesis: The synthesis of the first generation of polyA C H T U N G T R E N N U N G (llysine) was carried out by a three-step sequence (Scheme 2) by implementing the knowledge from our research group [17,28,29] and by starting from N-carbamoyl derivative CLysA C H T U N G T R E N N U N G (Tfa), which was prepared by a straightforward NcarbamA C H T U N G T R E N N U N G oylation of N e -trifluoroacetyl-l-lysine. [29] NO + O 2 -promoted nitrosation [28] of C-LysA C H T U N G T R E N N U N G (Tfa) in acetonitrile gave monomer LysA C H T U N G T R E N N U N G (Tfa)-NCA, which was then reacted in aqueous sodium hydrogen carbonate (pH 6.5) to give N e -protected oligoA C H T U N G T R E N N U N G (l-lysine) G1P.…”

“…[15] As an example based on peptide bonds, Klok et al [14,16] reported the synthesis of dendritic graft polyA C H T U N G T R E N N U N G (l-lysine)s by iterative co-polycondensation of two differently N e -protected amino acid N-carboxyanhydrides (NCA) in dimethylformamide, followed by the selective removal of one of these sets of protecting groups; a final, complete deprotection step then afforded the desired dendritic graft polyA C H T U N G T R E N N U N G (llysine). [14] Our recent investigations on NCA chemistry in water (in connection with their possible key role in the emergence of life through the prebiotic chemistry of peptides), [17][18][19] gave us the opportunity to address the synthesis of lysine arborescent polymer in an original manner. Because of their high Abstract in French: Nous dØcrivons la synthse et la caractØ-risation de nouvelles architectures arborescentes de polyA C H T U N G T R E N N U N G (llysine), nommØes dendrimres greffØs de lysine (DGL).…”