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, A devised loop allowing the formation and the reproduction of the 2'(3')-aminoacylated nucleotide 13 based on a facilitated intramolecular transfer of the aminoacyl moiety in mixed anhydrides 10 and on the possibility of cleavage of the phosphoramidate linkage of the resulting co-tetramer 11 into two 2, p.13

, Experimental procedures for chapter 5: Reagents and solvents were purchased from Sigma-Aldrich or Bachem, and were used without further purification. All aqueous solutions were prepared using pure water (18 M?) produced with a Milli-Q (Merck-Millipore) apparatus. NMR spectra in either DMSO, Scheme 7. Investigation of the possibility for intramolecular transfer of the 5'-aminoacyl moiety in the mixed anhydride copolymer 10 to the 2'(3')-OH, p.300

. Mhz, MHz); chemical shifts ?H are reported in ppm; coupling constants J are reported in Hz. In all the experiments, the pH was monitored using a Thermo Orion 3-STAR pH-meter with a VWR electrode, Bruker Avance, vol.500, p.3000

, B: CH3CN (0.1% TFA); flow rate 0.2 mL/min; gradient: 0 min (10% B) to 20 min (100% B). Method B: mobile phase made of solvent A: H2O (0.1% TFA, Standard system including an autosampler unit, p.5

, 10 min (10% B), 15 min (35%), 18 min (100% B), 19 min (100% B), pp.21-100

, mm 2.1×50 mm column (System B) or Thermo Scientific BDS-Hypersil C18 3 µm 50×2.1 mm column (System C). using gradients of solvent Method C: System B, mobile phase: A: H2O (0.1% formic acid, HPLC/ESI-MS analyses were carried out on a Waters Synapt G2-S mass spectrometer system connected to waters Acquity UPLC H-Class apparatus equipped with in an Aquity UPLC BEH C18, vol.1

D. Method, B: CH3CN (0.1% formic acid); flow rate 0.2 mL/min, System C, mobile phase solvent A: H2O (0.1% formic acid, p.15

, 18 min (100% B), 19 min (100% B), 25 min (100% B)

T. Baddiley, To a solution of dibenzyl phosphite (2.36 g, 9 mmol) in anhydrous toluene (30 mL), N-chloro succinimide (1.62 g, 12.1 mmol) was added. After stirring at room temperature for 2 hr, Synthesis of starting materials and reagents: Dibenzyl chlorophosphate, vol.2, 1947.

T. Baddiley, 2':3'-isoPropylidene adenosine (1 g, 3.25 mmol) was dissolved by warming in dry pyridine (12 mL), and the solution cooled in an acetone-liquid nitrogen bath until the liquid at sides of the flask began to solidify. Then subsequently, a solution of fresh dibenzyl chlorophosphate (2.66 g, 2.76 eq.) in toluene (2 mL) was added with shaking, and the mixture left for 3 hours in cold bath at a temperature just above the freezing point of the mixture under N2 gas and then set aside at room temperature overnight. Water (6 mL) and sodium carbonate (1 g) was added, and subsequently, the solution was evaporated under reduced pressure. The syrup obtained was dissolved in dichloromethane (100 mL), and the solution was washed with brine solution (3 × 100ml), then dried over Na2SO4, and concentrated to give a crude syrup. The crude syrup was chromatographed on silica gel (250 mL of CH2Cl2/MeOH = 97/3, 200 mL of CH2Cl2/MeOH = 95/5), then the fraction containing the product was evaporated to give an oily product (mass obtained 550 mg). HPLC analysis (method A): retention time 13, 1947.

, 31 P NMR (121 MHz, CDCl3) ? -0.88 (s)

. Esi-ms,

, Bn-5'-AMP, 4: A procedure from the literature (Baddiley and Todd, 1947) was modified as follows: the compound 3 (400 mg ,0.9 mmol) was dissolved in ethanol (0.27 mL), then a 9, p.27

, ml of 19 mM trifluoroacetic acid (1 eq.) was added, and the solution was refluxed for 90 min. Then the solvent was evaporated and then freeze-dried after the addition of water (mass obtained = 350 mg). HPLC analysis (method A): retention time 2, vol.9

H. Nmr, 300 MHz, D2O) ? 8.21 (s, 1H), 8.07 -7.96 (m, 1H), 7.09 (dd, J = 10, vol.9

. Liu, tertButyloxycarbonyl (Boc) Leucine (0.31 mmol) was dissolved in dimethylformamide (DMF, 0.125 mL). 1,1'-Carbonyldiimidazole (89.2 mg, 0.34 mmol) was added to the solution and allowed to react for 5 min at room temperature. The resulting solution of the imidazolide of amino acid was added to the 5'-benzyl AMP.Na salt (0.25 mmol) in water (0.25 mL). After reacting for one night. DMF was removed under vacuum. The mono nucleotide aminoacyl ester was isolated from the aqueous phase by preparative LC C18 column with the gradient: mobile phase: A: H2O + 5 mM triethylamine and acetic acid at pH 6.5, B: acetonitrile; flow rate: 9 mL/min; 0 min (10% B), to 21 min (60% B), and 22 min (100% B). The solvent was removed by lyophilization. The Boc protecting group was removed by trifluoroacetic acid (0.25 mL) for 10 min. The precipitate was collected by centrifugation after adding diethyl ether, 31 P NMR (121 MHz, D2O) ? 0.28 (s), HRMS (ESI -): calcd. for C17H19N5O7P, 1978.

, min; HRMS (ESI -): calcd. for C23H30N6O8P, 1858.

, regioisomer: 1 H NMR (300 MHz, D2O) ? 8.38 (s, 1H), 8.18 (s, 1H), 7.20 -7.00 (m, 5H), 6.01 (d, J = 6.8 Hz, 1H), vol.5

6. Hz, After three days at 5 °C (in the fridge), the mixture was separated by preparative HPLC with the gradient as follows: mobile phase: A: H2O + 5 mM triethylamine and acetic acid at pH 6.5, B: acetonitrile; flow rate: 9 mL/min; 0 min (10% B), to 12 min (15% B), to 17 min (23% B) and 18 min (100% B), 22 (100% B). The fraction containing the product was collected and the solvent was evaporated, then freeze dried after adding water (the product was contaminated by Nethyl-N'-(dimethyl)aminopropyl urea (EDU) present as a counter ion). The white powder (35 mg, Other signals for this compound were mainly obscured. Preparation of benzylated co-trimer: (N-2'(3')-Leucyl adenosine 5'-benzyl phosphate)-5'-adenosine phosphoramidate, vol.7

, Figure 3); 31 P NMR (D2O, 202 MHz, Figure 4) ? 6.77 (s), 6.38 (s), 0.02 (s)

. Esi-ms, Removal of the benzyl protecting group: co-trimer, 8: The removal of the benzyl group was done according to a procedure of the literature (Michelson and Todd 1949). (15 mg, 0.017 mmol) of compound 7 was dissolved in methanol (5.5 mL). An equal weight of 40 %, vol.62

, Then the hydrogenation proceeded overnight, and the mixture was filtered (using celite), washed with a mixture of methanol and water, and evaporated under reduced pressure. The product was used without further purification (white precipitate, mass obtained = 12 mg). HPLC analysis (method A): retention time 3 min, 4 min; HPLC analysis (method B): retention time 11, A gentle stream of nitrogen was passed through the reaction mixture for 15 mins, 1914.

L. , yield 24%). 1 H NMR (400 MHz, CDCl3) ? 6.69 (s, 1H, The N-carboxyanhydride was prepared by reaction of H-L-Leu-OH with triphospgene, vol.9, 1988.

, Procedures for the study of the reactivity of copolymers (8) with NCAs

J. Baddiley and A. R. Todd, Part I. Muscle Adenylic Acid and Adenosine Di phosphate, J. Chem. Soc, vol.0, pp.648-651, 1947.

J. Biron, A. L. Parkes, R. Pascal, and J. D. Sutherland, Expeditious, potentially primordial, aminoacylation of nucleotides, Angew. Chem. Int. Ed, vol.44, pp.6731-6734, 2005.

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A. M. Michelson and A. R. Todd, Part III. Mononucleotides derived from Adenosine, Guanosine, Cytidine, and Uridine, J. Chem. Soc, vol.0, pp.2476-2486, 1949.

A. Pross, What is Life? How Chemistry Becomes Biology, 2016.

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A. L. Weber and L. E. Orgel, The formation of peptides from the 2'(3')-glycyl ester of a nucleotide, J. Mol. Evol, vol.11, pp.189-198, 1978.

H. Nmr, 500 MHz, D 2 O) of trimer model 7 (bis-N-ethyl-N'-(dimethyl)aminopropyl urea salt)

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