1 Lohrmann, R. & Orgel, L. E. Prebiotic synthesis: phosphorylation in aqueous solution. Science 161, 64–66 (1968).

2 Schwartz, A. W. Specific phosphorylation of the 2′- and 3′-positions in ribonucleosides. J. Chem. Soc. D 1393a ( 1969).

3 Leman, L. J., Orgel, L. E. & Ghadiri, M. R. Amino acid dependent formation of phosphate anhydrides in water mediated by carbonyl sulfide. J. Am. Chem. Soc. 128, 20–21 (2006).

4 Powner, M. W., Gerland, B. & Sutherland, J. D. Synthesis of activated pyrimidine ribonucleotides in prebiotically plausible conditions. Nature 459, 239–242 (2009).

5 Burcar, B. et al. Darwin's warm little pond: a one-pot reaction for prebiotic phosphorylation and the mobilization of phosphate from minerals in a urea-based solvent. Angew. Chem. Int. Ed. 55, 13249–13253 (2016).

6 Kim, H. J. et al. Evaporite borate-containing mineral ensembles make phosphate available and regiospecifically phosphorylate ribonucleosides: borate as a multifaceted problem solver in prebiotic chemistry. Angew. Chem. Int. Ed. 55, 15816–15820 (2016).

7 Pasek, M. A. & Kee, T. P. in Origins of Life: The Primal Self-Organization (eds Egel, R., Lankenau, D.-H. & Mulkidjanian, A. Y.) 57–84 (Springer, 2011).

8 Gull, M. Prebiotic phosphorylation reactions on the early Earth. Challenges 5, 193–212 (2014).

9 Ruiz-Mirazo, K., Briones, C. & de la Escosura, A. Prebiotic systems chemistry: new perspectives for the origins of life. Chem. Rev. 114, 285–366 (2014).

10 Krishnamurthy, R., Guntha, S. & Eschenmoser, A. Regioselective α-phosphorylation of aldoses in aqueous solution. Angew. Chem. Int. Ed. 39, 2281–2285 (2000).

11 Coggins, A. J. & Powner, M. W. Prebiotic synthesis of phosphoenol pyruvate by α-phosphorylation-controlled triose glycolysis. Nat. Chem. 9, 310–317 (2017).

12 Meznik, L., Thomas, B. & Töpelmann, W. Zum Reaktionsverhalten von phosphoroxidtriamid in alkalischen lösungen. Zeit. Chemie 22, 211–211 (1982).

13 Richter, S., Töpelmann, W. & Lehmann, H.-A. Zur hydrolyse der phosphorsäureamide. Zeit. Anorg. Allgem. Chemie 424, 133–143 (1976).

14 Bishop, M. J., Lohrmann, R. & Orgel, L. E. Prebiotic phosphorylation of thymidine at 65 °C in simulated desert conditions. Nature 237, 162–164 (1972).

15 Lohrmann, R. & Orgel, L. E. Urea–inorganic phosphate mixtures as prebiotic phosphorylating agents. Science 171, 490–494 (1971).

16 Schoffstall, A. M. Prebiotic phosphorylation of nucleosides in formamide. Origins Life Evol. Biosph. 7, 399–412 (1976).

17 Cafferty, B. J., Fialho, D. M., Khanam, J., Krishnamurthy, R. & Hud, N. V. Spontaneous formation and base pairing of plausible prebiotic nucleotides in water. Nat. Commun. 7, 11328 (2016).

18 Bowler, F. R. et al. Prebiotically plausible oligoribonucleotide ligation facilitated by chemoselective acetylation. Nat. Chem. 5, 383–389 (2013).

19 Kervio, E., Sosson, M. & Richert, C. The effect of leaving groups on binding and reactivity in enzyme-free copying of DNA and RNA. Nucleic Acids Res. 44, 5504–5514 (2016).

20 Apel, C. L., Deamer, D. W. & Mautner, M. N. Self-assembled vesicles of monocarboxylic acids and alcohols: conditions for stability and for the encapsulation of biopolymers. Biochim. Biophys. Acta 1559, 1–9 (2002).

21 Gendaszewska-Darmach, E. & Drzazga, A. Biological relevance of lysophospholipids and green solutions for their synthesis. Curr. Org. Chem. 18, 2928–2949 (2014).

22 Dubois, M. & Zemb, Th . Swelling limits for bilayer microstructures: the implosion of lamellar structure versus ordered lamellae. Curr. Opin. Colloid Interface Sci. 5, 27–37 (2000).

23 Zhu, T. F. & Szostak, J. W. Exploding vesicles. J. Sys. Chem. 2, 4 (2011).

24 Lawless, J. G. & Yuen, G. U. Quantification of monocarboxylic acids in the Murchison carbonaceous meteorite. Nature 282, 396–398 (1979).

25 Szostak, J. W. An optimal degree of physical and chemical heterogeneity for the origin of life? Phil. Trans. R. Soc. Lond. B 366, 2894–2901 (2011).

26 Dhiman, R. S., Opinska, L. G. & Kluger, R. Biomimetic peptide bond formation in water with aminoacyl phosphate esters. Org. Biomol. Chem. 9, 5645–5647 (2011).

27 Knowles, J. Enzyme-catalyzed phosphoryl transfer reactions. Ann. Rev. Biochem. 49, 877–919 (1980).

28 Lassila, J. K., Zalatan, J. G. & Herschlag, D. Biological phosphoryl-transfer reactions: understanding mechanism and catalysis. Ann. Rev. Biochem. 80, 669–702 (2011).

29 Frederix, P. W. J. M. et al. Exploring the sequence space for (tri-)peptide self-assembly to design and discover new hydrogels. Nat. Chem. 7, 30–37 (2015).

30 Griesser, H. et al. Ribonucleotides and RNA promote peptide chain growth. Angew. Chem. Int. Ed. 56, 1219–1223 (2017).

31 Adamala, K. & Szostak, J. W. Competition between model protocells driven by an encapsulated catalyst. Nat. Chem. 5, 495–501 (2013).

32 Karki, M., Gibard, C., Bhowmik, S. & Krishnamurthy, R. Nitrogenous derivatives of phosphorus and the origins of life: plausible prebiotic phosphorylating agents in water. Life (Basel). 7, E32 (2017).

33 Lazcano, A. Complexity, self-organization and the origin of life: the happy liaison? Origins of Life 2009, 13–22 (2009).

34 Eschenmoser, A. The TNA-family of nucleic acid systems: properties and prospects. Orig. Life Evol. Biosph. 34, 277–306 (2004).

35 Anastasi, C. et al. The search for a potentially prebiotic synthesis of nucleotides via arabinose-3-phosphate and its cyanamide derivative. Chem. Eur. J. 14, 2375–2388 (2008).

36 Yamagata, Y., Watanabe, H., Saitoh, M. & Namba, T. Volcanic production of polyphosphates and its relevance to prebiotic evolution. Nature 352, 516–519 (1991).

37 Feldmann, W. & Thilo, E. Zur chemie der kondensierten Phosphate und Arsenate. XXXVIII. Amidotriphosphat. Zeit. Anorg. Allgem. Chemie. 328, 113–126 (1964).

38 Thilo, E. Zur strukturchemie der kondensierten anorganischen Phosphate. Angew. Chem. 77, 1056–1066 (1965).

39 Pasek, M. A. & Lauretta, D. S. Aqueous corrosion of phosphide minerals from iron meteorites: a highly reactive source of prebiotic phosphorus on the surface of the early Earth. Astrobiology 5, 515–535 (2005).

40 Bryant, D. E. & Kee, T. P. Direct evidence for the availability of reactive, water soluble phosphorus on the early Earth. H-Phosphinic acid from the Nantan meteorite. Chem. Commun. 2006, 2344–2346 (2006).

41 Turner, B. E. & Bally, J. Detection of interstellar PN: the first identified phosphorus compound in the interstellar medium. Astrophys. J. 321, L75–L79 (1987).

42 Ziurys, L. M. Detection of interstellar PN: the first phosphorous-bearing species observed in molecular clouds. Astrophys. J. 321, L81–L85 (1987).

43 Rivilla, V. M. et al. The first detections of the key prebiotic molecule PO in star-forming regions. Astrophys. J. 826, 161 (2016).