Thiophosphate – A Versatile Prebiotic Reagent?

Abstract

Described are our preliminary studies on the reactivity of thiophosphate in a setting which correlates with the cyanosulfidic systems chemistry we have previously reported. Thiophosphate adds to various nitrile groups giving the corresponding thioamides in a highly efficient manner and the mechanistic implications are briefly discussed. Thiophosphate can also act as a phosphorylating agent, which was demonstrated with adenosine. The prebiotic availability of thiophosphate must be questioned, but if a plausible synthesis can be found, the advantages it would bring to the field of prebiotic chemistry appear to be highly beneficial.

Key words

thiophosphate - thiolysis - phosphorylation - prebiotic chemistry - cyanosulfidic

• References and Notes

• 1 Patel BH, Percivalle C, Ritson DJ, Duffy CD, Sutherland JD. Nat. Chem. 2015; 7: 301
• 2a Ritson DJ, Sutherland JD. Nat. Chem. 2012; 4: 895
• 2b Ritson DJ, Sutherland JD. Angew. Chem. Int. Ed. 2013; 52: 5845
• 3a Nagyvary J, Provenzale RG. N.A.S. Autumn Meeting 1970; No. 4: 8A
• 3b Slabaugh MR, Harvey AJ, Nagyvary J. J. Mol. Evol. 1974; 3: 317
• 3c Kapovits I, Nagyvary J. J. Mol. Evol. 1978; 11: 25
• 4 Allen CM, Jones ME. Biochemistry 1964; 3: 1238
• 5a Jones ME, Lipmann F. Proc. Natl. Acad. Sci. U.S.A. 1960; 46: 1186
• 5b Lohrmann R, Orgel LE. Science 1968; 161: 64
• 6 Standard Procedure for Thiolysis Na₃PSO₃·xH₂O (≥90% purity, 0.320 mmol, 64 mg) was dissolved in degassed 10% D₂O in H₂O (0.5 mL) in an Eppendorf tube and the pH was lowered to 6.5 (5.0 in the case of 26) using degassed HCl. The nitrile was added (0.080 mmol), and the volume made up to 1 mL with degassed 10% D₂O. The reaction was sealed and heated at 50 °C for 24 h taking time points at 8 and 24 h.
• 7 Yields of identifiable compounds after 24 h: thioformamide 51%, formamide 6%, cyanoformamide 2%, thiocyanate 8%.

For example, see:
• 8a Ferris JP, Orgel LE. J. Am. Chem. Soc. 1965; 87: 4976
• 8b Zubay G, Mui T. Orig. Life. Evol. Biosph. 2001; 31: 87

For example, see:
• 9a Eschenmoser A. Angew. Chem., Int. Ed. Engl. 1988; 27: 5
• 9b Eschenmoser A, Loewenthal E. Chem. Soc. Rev. 1992; 21: 1
• 9c Raffaelli N In Origins of Life: The Primal Self-Organisation . Egel R, Lankenau D, Mulkidjanian AY. Springer; Berlin: 2011: 185
• 10 Schoffstall AM. Orig. Life Evol. Biosph. 1976; 7: 399
• 11 At a concentration of 100 mM, pH 6.5 and at r.t., thiophosphate has a half-life of ca. 17 d.
• 12 Schwartz AW In Molecular Evolution – Prebiological and Biological . Oparin AI, Rohlfing DL. Springer; New York: 1972: 129
• 13 Pasek MA, Lauretta DS. Astrobiol. 2005; 5: 515
• 14 Bryant DE, Kee TP. Chem. Commun. 2006; 2344
• 15 Lönnberg T. Beilstein J. Org. Chem. 2016; 12: 670