Utility of azolium triflates as promoters for the condensation of a nucleoside phosphoramidite and a nucleoside in the Agrawal's stereoselective synthesis of nucleoside phosphorothioates

European Journal of Organic Chemistry

Volumn , Issue 24, 2005, Pages 5216-5223

  Hyodo, Mamoru ^a   Ando, Hirotaka ^a   Nishitani, Hisashi ^a   Hattori, Akira ^a   Hayakawa, Hiroyuki ^a   Kataoka, Masanori ^a   Hayakawa, Yoshihiro ^a  

^a NAGOYA UNIVERSITY   (Japan)

Author keywords

Chirality; Nitrogen heterocycles; Oligonucleotides; Phosphoramidite; Solid phase synthesis

Indexed keywords

EID: 30044451389     PISSN: 1434193X     EISSN: None     Source Type: Journal    
DOI: 10.1002/ejoc.200500403     Document Type: Article

References (25)

1. a) E. Uhlmann, A. Peyman, Chem. Rev. 1990, 90, 543-584;
2. b) J. F. Milligan, M. D. Matteucci, J. C. Martin, J. Med. Chem. 1993, 36, 1923-1937;
3. c) R. S. Varma, Synlett 1993, 621-637;
4. d) W. J. Stec, A. Wilk, Angew. Chem. Int. Ed. Engl. 1994, 33, 709-722.
5. a) R. P. Iyer, M.-J. Guo, D. Yu, S. Agrawal, Tetrahedron Lett. 1998, 39, 2491-2494;
6. b) D. Yu, E. R. Kandimalla, A. Roskey, Q. Zhao, L. Chen, J. Chen, S. Agrawal, Bioorg. Med. Chem. 2000, 8, 275-284.
7. a) Y. Jin, G. Biancotto, G. Just, Tetrahedron Lett. 1996, 37, 973-976;
8. b) Y. Jin, G. Just, J. Org. Chem. 1998, 63, 3647-3654;
9. c) Y. Lu, G. Just, Tetrahedron 2001, 57, 1677-1687.
10. a) Y. Lu, G. Just, Angew. Chem. Int. Ed. 2000, 39, 4521-4524;
11. b) Y. Lu, G. Just, Tetrahedron 2000, 56, 4355-4365.
12. a) N. Oka, T. Wada, K. Saigo, J. Am. Chem. Soc. 2002, 124, 4962-4963;
13. b) N. Oka, T. Wada, K. Saigo, J. Am. Chem. Soc. 2003, 125, 8307-8317.
14. The Agrawal method forms the nucleoside phosphorothioate via the 1H-tetrazole-promoted condensation of the nucleoside 3′- oxazaphospholidine, Rc-1 or Sc-2, and a 5′-O-free nucleoside, followed by stereospecific sulfurization as key reactions. According to the reported data, the stereoselectivity in the solid-phase preparation of the Sp-dithymidine phosphorothioate Sp-4d using Sc-2d as the building unit by means of the existing Agrawal strategy is in 80% de. By contrast, the synthesis of the related Sp-dithymidine phosphorothioate according to the Wada method, which is the best existing method for gaining high stereoselectivity, gave this target product in >98% de.
15. a) V. Sum, C. A. Baird, T. P. Kee, M. Thornton-Pett, J. Chem. Soc. Perkin Trans. 1 1994, 3183-3200;
16. b) J. V. Carey, M. D. Barker, J. M. Brown, M. J. H. Russell, J. Chem. Soc. Perkin Trans. 1 1993, 831-839.
17. A. Wilk, A. Grajkowski, T. E. Bull, A. M. Dixon, D. I. Freedberg, S. L. Beaucage, J. Am. Chem. Soc. 2002, 124, 1180-1181.
18. H. Arzoumanian, G. Buono, M. Choukrad, J.-F. Petrignani, Organometallics 1988, 7, 59-62.
19. Y. Hayakawa, T. Iwase, E. J. Nurminen, M. Tsukamoto, M. Kataoka, Tetrahedron 2005, 61, 2203-2209.
20. a) Y. Hayakawa, R. Kawai, A. Hirata, J. Sugimoto, M. Kataoka, A. Sakakura, M. Hirose, R. Noyori, J. Am. Chem. Soc. 2001, 123, 8165-8176;
21. b) Y. Hayakawa, M. Kataoka, R. Noyori, J. Org. Chem. 1996, 61, 7996-7997.
22. A. Ohkubo, K. Seio, M. Sekine, Tetrahedron Lett. 2004, 45, 363-366.
23. M. Hyodo, Y. Sato, S. Yamashita, A. Hattori, E. Kambe, M. Kataoka, Y. Hayakawa, Tetrahedron 2005, 61, 965-970.
24. W. J. Stec, A. Grajkowski, A. Kobylanska, B. Karwowski, M. Koziolkiewicz, K. Misiura, A. Okruszek, A. Wilk, P. Guga, M. Boczkowska, J. Am. Chem. Soc. 1995, 117, 12019-12029.
25. K. K. Ogilvie, Can. J. Chem. 1973, 51, 3799-3807.