N-Phosphoryl Amino Acids and Biomolecular Origins. Review Paper in Honor of the 50th Anniversary of the Publication of ``A Production of Amino Acids under Possible Primitive Earth Conditions'' (Miller, 1953)

Abstract

The possible role of phosphoryl amino acids for biomolecular origins is briefly reviewed. Peptide formation, ester formation, ester exchange on phosphorus and N to O migration occurred when the N-phosphoryl amino acid was incubated at room temperature. Short nucleotides and peptides were formed when nucleoside was reacted with N-phosphoryl amino acid at room temperature. Serine and threonine residues in their conjugate with different nucleosides (mediated with phosphorus) showed different self-cleavage activities. N-phosphoryl Histine and Ser-His dipeptide could cleave nucleic acids, proteins and esters in neutral medium. Based on a simple model, a pathway of 'co-evolution of protein and nucleic acid' was proposed.

From Interstellar Amino Acids to Prebiotic Catalytic Peptides: A Review

“…N-Phosphoryl a-amino acids lead to oligopeptides via a five-membered cyclic pentacoordinate phosphoric-carboxylic mixed anhydrides resembling the N-carboxyanhydrides [54].…”

5. Prebiotic Chemistry – Biochemistry – Emergence of Life (4.4–2 Ga)

“…N-(dialkylphosphoryl)amino acids display interesting capabilities for the prebiotic syntheses of peptides and polynucleotides (Cheng et al, 2004). An intramolecular phosphoric-carboxylic mixed anhydride has been proposed to explain the specific behavior of N-(dialkylphosphoryl)amino acids that spontaneously give oligopeptides upon standing in various solvents (Figure 5.5).…”

Synthesis and characterization of new 1H-pyrazolo[3,4-b]pyridine phosphoramidate derivatives

“…12 In this context, heterocyclic linked to other biologically active molecules, like, e.g., phosphoramidates, can give rise to new derivatives with potential biological applications. [13][14][15][16][17][18] Introduction of a phosphoramidate group essentially changes the physical and chemical properties of the parent molecule, resulting in the The aminoalkylphosphoramidates 7a-d were synthesized from diisopropylphosphonate 5 and aliphatic diamines 6a-d. 25,26 In order to guarantee monophosphorylation of the diamines, at least 2.5-fold excess of diamine in ethanol were used. Keeping alkaline pH and temperature below 55 °C is required to avoid bis-phosphorylation.…”

“…The presence of an electronwithdrawing group (-CO 2 Et) in 5-position of the substrate 4 and the excess of the nucleophilic agent 7 facilitate the reaction. The products were fully characterized by infrared, 1 H, 13 C, and 31 P NMR spectroscopies and by high resolution mass spectrometry (HRMS). [3,4-b]pyridine phosphoramidates 8a-l showed in their decoupled 31 P NMR spectra one signal in the region between 7.01-7.60 ppm, typical for phosphoramidates.…”