Benzimidazolium triflate as an efficient promoter for nucleotide synthesis via the phosphoramidite method

Journal of Organic Chemistry

Volumn 61, Issue 23, 1996, Pages 7996-7997

  Hayakawa, Yoshihiro ^a   Kataoka, Masanori ^a   Noyori, Ryoji ^a  

^a NAGOYA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

BENZIMIDAZOLE DERIVATIVE; OLIGODEOXYRIBONUCLEOTIDE;

ARTICLE; DRUG SYNTHESIS; REACTION ANALYSIS; TECHNIQUE;

EID: 0029843242     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo961569e     Document Type: Article

References (21)

1. Beaucage, S. L.; Iyer, R. P. Tetrahedron 1993, 49, 6123-6194 and references cited therein.
2. Beaucage, S. L.; Caruthers, M. H. Tetrahedron Lett. 1981, 22, 1859-1862.
3. (a) Froehler, B. C.; Matteucci, M. D. Tetrahedron Lett. 1983, 24, 3171-3174.
4. (b) Pon, R. T. Tetrahedron Lett. 1987, 28, 3643-3646.
5. Vinayak, R.; Colonna, F.; Tsou, D.; Mullah, B.; Andrus, A.; Sproat, B. Nucleic Acids Symp. Ser. 1994, 31, 165-166.
6. (a) Uhlmann, E.; Peyman, A. Chem. Rev. 1990, 90, 543-584.
7. (b) Milligane, J. F., Matteucci, M. D.; Martin, J. C. J. Med. Chem. 1993, 36, 1923-1937.
8. (c) Varma, R. S. Synlett 1993, 621-637.
9. (d) Stec, W. J.; Wilk, A. Angew. Chem., Int. Ed. Engl. 1994, 33, 709-722.
10. Pyridinium tetrafluoroborates and N-methylimidazolium trifluoroacetate are used as the activator for the weakly reactive amidites including the phosphorothioamidite, but these reagents cause considerable cleavage of the dimethoxytrityl protector. See: Brill, W. K.-D.; Nielsen, J.; Caruthers, M. H. J. Am. Chem. Soc. 1991, 113, 3972-3980.
11. Hayakawa, Y.; Uchiyama, M.; Noyori, R. Tetrahedron Lett. 1986, 27, 4191-4194.
12. Use of benzimidazolium mesylate, mp 214-215 °C, less soluble in acetonitrile (<0.1 mol/L), usually completes the reaction of o-chlorophenyl phosphoramidites within 45 min. Benzimidazolium to-sylate, mp 222-223 °C, is scarcely soluble in acetonitrile.
13. (a) Dahl, B. H.; Nielsen, J.; Dahl, O. Nucleic Acids Res. 1987, 15, 1729-1743.
14. (b) Schwarz, M. W.; Pfleiderer, W. Tetrahedron Lett. 1984, 25, 5513-5516.
15. In usual cases, the reaction requires 2-4 equiv of a promoter for gaining an acceptable reaction rate. See: Stec, W. J.; Zon, G. Tetrahedron Lett. 1984, 25, 5279-5282.
16. (a) Hayakawa, Y.; Kato, H.; Uchiyama, M.; Noyori, R. J. Org. Chem. 1986, 51, 2400-2402.
17. (b) Hayakawa, Y.; Wakabayashi, S.; Kato, H.; Noyori, R. J. Am. Chem. Soc. 1990, 112, 1691-1696.
18. (a) Barone, A. D.; Tang, J. Y.; Caruthers, M. H. Nucleic Acids Res. 1984, 12, 4051-4061.
19. (b) Berner, S.; Mühlegger, K.; Seliger, H. Nucleic Acids Res. 1989, 17, 853-864.
20. 2O).
21. Sigma-Aldrich Library of Chemical Safety 2; Sigma-Aldrich: Milwaukee, 1990; p 3313D (Sigma-Aldrich Material Safety Data Sheets; Product No. 33644-0).