Biopolym. Cell. 2007; 23(6):538-544.
Bioorganic Chemistry
Synthesis of (2'-5')-triadenylate and their analogues using O-nucleophilic catalysis of internucleotide coupling reaction
- Institute of Molecular Biology and Genetics, NAS of Ukraine
150, Akademika Zabolotnoho Str., Kyiv, Ukraine, 03680
Abstract
(2'-5')-triadenylate and its analogues containing 3'-terminal epoxyadenosine or cordycepin residue were obtained by phosphotriester approach in the presence of 4-ethoxypyridine N-oxide (EPO) as O-nucleophilic catalyst of coupling reaction. The coupling reactions proceeded with high speed (below 5 min) and efficiency (yield 86–92 %). The reaction yields achieved in the presence of N-methylimidazole were substantially lower (80–85 %), and the final yields of triadenylates were only 21–25 %, as compared to 29–35 % obtained with N-oxide.
Keywords: (2'-5')-oligoadenylates, oligonucleotide analogues, phosphotriester synthesis, nucleophilic catalysis, pyridine N-oxides
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References
[1]
Player MR, Torrence PF. The 2-5A system: modulation of viral and cellular processes through acceleration of RNA degradation. Pharmacol Ther. 1998;78(2):55-113.
[2]
Adah SA, Bayly SF, Cramer H, Silverman RH, Torrence PF. Chemistry and biochemistry of 2',5'-oligoadenylate-based antisense strategy. Curr Med Chem. 2001;8(10):1189-212.
[3]
Malmgaard L. Induction and regulation of IFNs during viral infections. J Interferon Cytokine Res. 2004;24(8):439-54.
[4]
Liang SL, Quirk D, Zhou A. RNase L: its biological roles and regulation. IUBMB Life. 2006;58(9):508-14.
[5]
Castelli J, Wood KA, Youle RJ. The 2-5A system in viral infection and apoptosis. Biomed Pharmacother. 1998;52(9):386-90.
[6]
Lesiak K, Torrence PF. Efficient functionalization of 2',5'-oligoadenylates with sulfur. Bioconjug Chem. 1997;8(2):199-203.
[7]
Ueno Y, Ishihara S, Ito Y, Kitade Y. Synthesis of 2',5'-oligoadenylate analogs containing an adenine acyclonucleoside and their ability to activate human RNase L. Bioorg Med Chem Lett. 2004;14(17):4431-4.
[8]
Pat. EP156870. Novel 2',5'-oligoadenylic acids analogues. M. Kozumi, K. Morita. Publ. 2005.
[9]
Ueno Y, Kato Y, Okatani S, Ishida N, Nakanishi M, Kitade Y. Synthesis of Antisense Oligonucleotides Carrying Modified 2-5A Molecules at Their 5‘-Termini and Their Properties. Bioconjug Chem. 2003;14(3):690–6.
[10]
Sawai H, Hirano A, Mori H, Shinozuka K, Dong B, Silverman RH. Synthesis, characterization, and biological properties of 8-azido- and 8-amino-substituted 2',5'-oligoadenylates. J Med Chem. 2003;46(23):4926-32.
[11]
Kalinichenko EN, Podkopaeva TL, Budko EV, Seela F, Dong B, Silverman R, Veps?l?inen J, Torrence PF, Mikhailopulo IA. 3-Deazaadenosine analogues of p5'A2'p5'A2'p5'A: synthesis, stereochemistry, and the roles of adenine ring nitrogen-3 in the interaction with RNase L. Bioorg Med Chem. 2004;12(13):3637-47.
[12]
Pat. USA 5571799. (2'-5')Oligoadenylate analogues useful as inhibitors of host-vs. graft response. Z. Tkachuk, E. Kvasyuk, G. Matsuka, I. Mikhailopulo. Publ. 1996.
[13]
Sidorik LL, Dubei IYa, Bobyk VI, Kozlov AV, Fadorkova OM, Kovenya TV, Ryabenko DV, Sergienko OV, Trunina IV, Pogrebnoi PV, MAtsuka GKh. Therapeutic effects of the action of various doses of 2'-5'-oligoadenylate on experimental myosin-induced myocardial damage. Dopovidi Nats Akad Nauk Ukrainy. 2001; (9):161-5.
[14]
Tkachuk ZYu, Dubey IYa, Yakovenko TG, Semernikova LI, Shapoval SO, Artemenko VS, Dubey LV. Synthesis of 2’-5’-oligoadenylates and study on their effect on proliferation and migration of bone marrow stem cells of mice in vitro and in vivo. Biopolym Cell. 2007; 23(1):14-20.
[15]
Tkachuk ZYu, Tkachuk VV, Tkachuk LV, Semernikova LI, Matsuka GKh. Influence of 2', 5' oligoadenylates and theirs analogues on the cyclic nucleotides level in vivo and in vitro. Biopolym Cell. 2001; 17(5):411-6.
[16]
M?ller WE, Weiler BE, Charubala R, Pfleiderer W, Leserman L, Sobol RW, Suhadolnik RJ, Schr?der HC. Cordycepin analogues of 2',5'-oligoadenylate inhibit human immunodeficiency virus infection via inhibition of reverse transcriptase. Biochemistry. 1991;30(8):2027-33.
[17]
Pat. USA 5550111. Dual action 2',5'-oligoadenylate antiviral derivatives and uses thereof. R. J. Suhadolnik, W. Pfleiderer. Publ. 1996.
[18]
Black PL, Henderson EE, Pfleiderer W, Charubala R, Suhadolnik RJ. 2',5'-Oligoadenylate trimer core and the cordycepin analog augment the tumoricidal activity of human natural killer cells. J Immunol. 1984;133(5):2773-7.
[19]
Hubbell HR, Pequignot EC, Willis DH, Lee C, Suhadolnik RJ. Differential antiproliferative actions of 2',5' oligo A trimer core and its cordycepin analogue on human tumor cells. Int J Cancer. 1985;36(3):389-94.
[20]
Savelova VA, Belousova LA, Litvinenko LM, Iakovets AA. Comparison of the nucleophilic reactivity of 4-N, N-dimethylaminopyridin with the nucleophilic reactivity of its N-oxyde. Dokl Akad Nauk SSSR. 1984; 274(6):1393-8.
[21]
Efimov VA, Chakhmakhcheva OG, Ovchinnikov YuA. Improved rapid phosphotriester synthesis of oligodeoxyribonucleotides using oxygen-nucleophilic catalysts. Nucleic Acids Res. 1985;13(10):3651-66.
[22]
Efimov VA, Buryakova AA, Dubey IY, Polushin NN, Chakhmakhcheva OG, Ovchinnikov YuA. Application of new catalytic phosphate protecting groups for the highly efficient phosphotriester oligonucleotide synthesis. Nucleic Acids Res. 1986;14(16):6525-40.
[23]
Efimov VA, Buryakova AA, Polushin NN, Dubey IY, Chakhmakhcheva OG, Ovchinnikov YA. Phosphotriester synthesis of oligonucleotides with the Use of N- and O-nucleophilic intramolecular catalysis. Nucleosides Nucleotides. 1987;6(1-2):279–82.
[24]
Ochiai E. Recent japanese work on the chemistry of pyridine 1-oxide and related compounds. J Org Chem. 1953;18(5):534–51.
[25]
Katritzky A. R. The preparation of some substituted pyridine 1-oxides. J Chem Soc. 1956. 7: 2404-8. ttp://
[26]
Kyasyuk EI, Kulak TI, Khripach NB, Mikhailopulo IA, Uhlmann E, Charubala R, et al. Nucleotides XXIV; 1 Preparative Synthesis of Trimeric (2?-5?) Oligoadenylic Acid . Synthesis. 1987;1987(06):535–41.
[27]
AS. SSSR 1541214. A method of producing 5'-O-monomethoxytrityl-N6,3'-O-dibenzoiladenozina. TL Podkopayeva, YeN Kalinichenko, IA Mikhaylopulo. BI. 1990. (5): 121.
[28]
Oligonucleotide synthesis: a practical approach. Ed. M. J. Gait. Oxford: IRL press, 1984. 218 p.
[29]
Robins MJ, Fouron Y, Mengel R. Nucleic acid related compounds. 11. Adenosine 2',3'-ribo-epoxide. Synthesis, intramolecular degradation, and transformation into 3'-substituted xylofuranosyl nucleosides and the lyxo-epoxide. J Org Chem. 1974;39(11):1564-70.
[30]
Reese CB, Zard L. Some observations relating to the oximate ion promoted unblocking of oligonucleotide aryl esters. Nucleic Acids Res. 1981;9(18):4611-26.
[31]
Efimov VA, Reverdatto SV, Chakhmakhcheva OG. New effective method for the synthesis of oligonucleotides via phosphotriester intermediates. Nucleic Acids Res. 1982;10(21):6675-94.
