Thiophosphate – A Versatile Prebiotic Reagent?
Received: 01 August 2016
Accepted after revision: 11 October 2016
27 October 2016 (eFirst)
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.
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%.
- 8a Ferris JP, Orgel LE. J. Am. Chem. Soc. 1965; 87: 4976
- 8b Zubay G, Mui T. Orig. Life. Evol. Biosph. 2001; 31: 87
- 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
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For example, see: