Stability of 3', 5'-o-(tetraisopropyldisiloxane-1,3-diyl)nucleosides in the presence of lewis acids

Trimethylsilyl trifluoromethanesulfonate catalyzes effective isomerization of 3',5'-O-(tetraisopropyldisiloxane1,3-diyl,TIPDS)nucleosides in 1,2-dicloroethane at 0C into 2',3'-O-TIPDS-derivatives to give 55-90% yields. On the other hand 3',5'-O-TIPDS-nucleosides except for uridine derivative 1a were found to be stable in the in the presence of tin tetrachloride and boron trifluoride etherate

защитные группы нуклеозидов, изомеризация, 3′,5′-O-(тетраизопропилдисилоксан-1,3-диил)нуклеозиды, триметилсилилтрифторметан-сульфонат.

1. Markiewicz, W. T. Tetraisopropyldissiloxane-1,3-diyl, a group for simultaneous protection of 3'-and 5'-hydroxy functions of nucleosides / W. T. Markiewicz // J. Chem. Res. (S). – 1979. – P. 24–25; (M). – 1979. – P. 187–194.

2. Markiewicz, W. T. Simultaneous protection of 3- and 5-hydroxyl groups of nucleosides. In Nucleic Acid Chemistry. Improved and New Synthetic Procedures and Techniques / W. T. Markiewicz, M. Wiewiorowski // Ed. L. B. Townsend, R. S. Tipson. J. Wiley & Sons. – New York, 1986; Part 3. – P. 229–231.

3. An efficient synthesis and physico-chemical properties of 2'-O-D-ribofuranosylnucleosides, minor tRNA components / S. N. Mikhailov, E. V. Efimtseva, G. V. Gurskaya, V. E. Zavodnik, A. De Bruyn, J. Rozenski, P. Herdewijn // J. Carbohydr. Chem. – 1997. – Vol. 16, № 1. – P. 75–92.

4. Markiewicz, W. T. Protection of vicinal trans-diol with tetraisopropyldisiloxane-1,3-diyl group / W. T. Markiewicz // Chemica Scripta. – 1986. – Vol. 26. – P. 123–125.

5. The reaction of 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane with cytosine arabinoside and 1-(6- deoxy--L-talofuranosyl)uracil / W. T. Markiewicz, N. Sh. Padyukova, Z. Samek, J. Smrt // Collection Czech. Chem. Comm. – 1980. – Vol. 45. – P. 1860–1865.

6. Wuts, P. G. 1,3-(1,1,3,3-Tetraisopropyldisiloxanylidene) derivative. In Greene’s Protective Groups in Organic Synthesis / P. G. M. Wuts, T. W Greene // Ed. J. Wiley & Sons. – Hoboken, 2007. – P. 356–360.

7. Efimtseva, E. V. Disaccharide nucleosides and oligonucleotides on their basis. New tools for the study of enzymes of nucleic acid metabolism. / E. V. Efimtseva, S. N. Mikhailov // Biochemistry (Moscow). – 2002. – Vol. 67. – P. 1136–1384.

8. Synthesis of RNA containing O-β-D-ribofuranosyl-(1''-2')-adenosine-5''-phosphate and 1-methyladenosine, minor components of tRNA. In Frontiers in Nucleosides and Nucleic Acids / K. Nauwelaerts, E. V. Efimtseva, S. N. Mikhailov, P. Herdewijn // Ed. R. F. Schinazi, D. C. Liotta. IHL Press. – Tucker USA, 2004. – P. 187–220.

9. Eфимцева, E. В. Дисахаридные нуклеозиды / E. В. Eфимцева, С. Н. Михайлов // Успехи химии. – 2004. – Т. 73. – С. 435–448.

10. Efimtseva, E. V. Disaccharide nucleosides and their incorporation into oligonucleotides / E. V. Efimtseva, I. V.Kulikova, S. N. Mikhailov // Current Org. Chem. – 2007. – Vol. 11, № 4. – P. 337–354.

11. Formation of trisaccharide nucleosides during disaccharide nucleoside synthesis / S. N. Mikhailov, A. A. Rodionov, E. V. Efimtseva, B. S. Ermolinsky, M. V. Fomitcheva, N. Sh. Padyukova, K. Rothenbacher, E. Lescrinier, P. Herdewijn // Eur. J. Org. Chem. – 1998. – P. 2193–2199.

12. Vorbrüggen, H. Silyl Hilbert-Jonson reaction in the presence of Friedel-Crafts catalysts. In Handbook of Nucleoside Synthesis / H. Vorbrüggen, C. Ruh-Pohlenz // Ed. J. Wiley & Sons. – New York, 2001. – P. 10–33.

13. Mikhailov, S. N. Synthesis of 2'-O-β-D-ribofuranosylnucleosides. In Current Protocols in Nucleic Acid Chemistry / S. N. Mikhailov, E. V. Efimtseva, A. A. Rodionov, G. V. Bobkov, I. V. Kulikova, P. Herdewijn // Ed. J. Wiley & Sons. – Hoboken, 2006. – Suppl. 27, Unit 1.14.1–1.14.19.

14. Acid-catalysed isomerization of the tetraisopropyldisiloxane-1,3-diyl group. Simultaneous protection of two secondary alcoholic function / C. H. M. Verdegaal, P. L. Jansse, J. F. M. de Rooij, J. H. van Boom // Tetrahedron Lett. – 1980. – Vol. 21. – P. 1571–1574.

15. Markiewicz, W. T. Transformation of rings containing tetraisopropyldisiloxane-1,3-diyl group – an equilibrium process enlarging the scope of applications of the group / W. T. Markiewicz, A. Bartoszuk // Bull. Polish Acad. Sci. – 1984. – Vol. 32. – P. 453–461.

16. Nucleic acid compounds. 41. Restricted furanose conformations of 3,5-O-(1,1,3,3-tetraisopropyldisilox-1,3-diyl)nucleosides provide a convenient evaluation of anomeric configuration / M. J. Robins, J. S. Wilson, L. Sawyer, M. N. G. James // Can. J. Chem. – 1983. – Vol. 61. – P. 1911–1920.

17. Davies, D. B. Conformations of nucleosides and nucleotides / D. B. Davies // Progress NMR Spectroscopy. – 1978. – Vol. 12. – P. 135–225.