- Concurrent Prebiotic Formation of Nucleoside-Amidophosphates and Nucleoside-Triphosphates Potentiates Transition from Abiotic to Biotic Polymerization
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Polymerization of nucleic acids in biology utilizes 5′-nucleoside triphosphates (NTPs) as substrates. The prebiotic availability of NTPs has been unresolved and other derivatives of nucleoside-monophosphates (NMPs) have been studied. However, this latter approach necessitates a change in chemistries when transitioning to biology. Herein we show that diamidophosphate (DAP), in a one-pot amidophosphorylation-hydrolysis setting converts NMPs into the corresponding NTPs via 5′-nucleoside amidophosphates (NaPs). The resulting crude mixture of NTPs are accepted by proteinaceous- and ribozyme-polymerases as substrates for nucleic acid polymerization. This phosphorylation also operates at the level of oligonucleotides enabling ribozyme-mediated ligation. This one-pot protocol for simultaneous generation of NaPs and NTPs suggests that the transition from prebiotic-phosphorylation and oligomerization to an enzymatic processive-polymerization can be more continuous than previously anticipated.
- Arriola, Joshua T.,Jiménez, Eddy I.,Krishnamurthy, Ramanarayanan,Lin, Huacan,Müller, Ulrich F.
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- Supported Synthesis of Adenosine Nucleotides and Derivatives on a Benzene-Centered Tripodal Soluble Support
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The first soluble-phase synthesis of adenosine nucleotides including α,β and β,γ-methylene bisphosphonate analogues on a multi-pod support is reported. Anchoring of a 2’,3’-protected purine nucleoside to the tripodal support via the nucleobase was successfully achieved using a microwave assisted Cu(I)-catalyzed azide-alkyne cycloaddition. Then, phosphorylation was performed, followed by cleavage with aqueous ammonia to provide adenine derivatives, and finally deprotection. When using benzylamine instead of ammonia, a derivative with N6-benzylamine adenine as nucleobase was obtained. This methodology allows to access adenosine 5’-mono, di and triphosphates, as well as various analogues of pharmacological interest in modest to good yields.
- Appy, Lucie,Peyrottes, Suzanne,Roy, Béatrice
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- Efficient synthesis of nucleoside 5′-triphosphates and their β,γ-bridging oxygen-modified analogs from nucleoside 5′-phosphates
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Thirteen nucleoside 5′-triphosphates (NTPs) and their β,γ-bridging oxygen-modified analogs (β,γ-CX 2-NTPs, X = H, F, Cl, and Br) have been efficiently synthesized from nucleoside 5′-phosphoropiperidates with 4,5-dicyanoimidazole as the activator. A high-yielding and chromatography-free protocol for the preparation of both natural and base-modified nucleoside 5′-phosphoropiperidates from the corresponding nucleoside 5′-phosphates was also developed.
- Sun, Qi,Gong, Shanshan,Sun, Jian,Wang, Chengjun,Liu, Si,Liu, Guodong,Ma, Cha
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supporting information
p. 2114 - 2118
(2014/04/03)
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- A P(V)-N activation strategy for the synthesis of nucleoside polyphosphates
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A general and high-yielding synthesis of nucleoside 5′-triphosphates (NTPs) and nucleoside 5′-diphosphates (NDPs) from protected nucleoside 5′-phosphoropiperidates promoted by 4,5-dicyanoimidazole (DCI) has been developed. 31P NMR tracing experiments showed that the sequential deprotection and coupling reactions were exceptionally clean. The phosphoropiperidate exhibited superior reactivity to the conventional phosphoromorpholidate toward DCI-promoted NTP/NDP synthesis. The experimental results suggested that the mechanism of DCI activation could be distinctive for NTP and NDP synthesis, depending on the different nucleophilicity of pyrophosphate and phosphate.
- Sun, Qi,Gong, Shanshan,Sun, Jian,Liu, Si,Xiao, Qiang,Pu, Shouzhi
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p. 8417 - 8426
(2013/09/24)
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- Convenient synthesis of nucleoside 5′-triphosphates for RNA transcription
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By generating a selective phosphitylating reagent in situ, nucleoside 5′-triphosphates can be conveniently synthesized in one pot. This novel strategy without nucleoside protection has been developed to largely simplify synthesis of the nucleoside triphosphates. This demonstrated principle can be applied to the 5′-triphosphate synthesis of both native and modified nucleosides.
- Caton-Williams, Julianne,Lin, Lina,Smith, Matthew,Huang, Zhen
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experimental part
p. 8142 - 8144
(2011/08/21)
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- A Novel Synthesis of Nucleoside 5'-Triphosphates
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Facile syntheses of ribonucleoside 5'-triphosphates have been accomplished in good yield (>60percent) in a one-pot reaction of unprotected nucleosides with phosphoryl chloride followed by treatment of the resulting phosphorodichloridate with tri-n-butylammonium phosphate in the presence of dimethylformamide.
- Mishra, Nrusingha C.,Broom, Arthur D.
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p. 1276 - 1277
(2007/10/02)
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- SYNTHESIS, STRUCTURE, PROTON-NUCLEAR MAGNETIC RESONANCE, AND FOURIER TRANSFORM INFRARED SPECTROSCOPY OF SEVERAL TRANSITION AND NONTRANSITION METAL-ADENOSINE-5-TRIPHOSPHATE COMPLEXES
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Several complexes of adenosine-5-triphosphate disodium salt (Na2H2ATP) with the metal ions, Na(1+), Mg(2+), Ca(2+), Mn(2+), Co(2+), Ni(2+), Cu(2+), and cis- and trans-Pt(NH3)2Cl2 and K2PtCl4 at pH = 3.5 and 7.2 have been isolated, identified, and studied.Marked spectral similarities have been observed for the structurally known metal-phosphate bonded compounds, 2.7H2O and 2.4H2O and all the metal-ATP complexes studied here, except the Pt-ATP complexes.The metal binding is through the α, β, and γ phosphate oxygen atoms when the N1-position of adenine is protonated.Spectral changes have also been observed for the Pt-ATP complexes in which there is a Pt-N7 and -N1 coordination.The sugar pucker in the Na2H2ATP.3H2O crystal dimers is C3'-endo-anti (in one) and C2'-endo-anti (in the other) with a characteristic infrared band at 818 cm-1.In the corresponding Cu(2+) and Zn(2+) complexes the sugar has C3'-endo-anti conformation with the marker band at about 814 cm-1.The C2'-endo-anti conformation is observed for all the metal-ATP complexes prepared here with a marker band at 825-822 cm-1.
- Tajmir-Riahi, H. A.,Bertrand, M. J.,Theophanides, T.
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p. 960 - 966
(2007/10/02)
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