N3′→P5′ Oligodeoxyribonucleotide Phosphoramidates: A New Method of Synthesis Based on a Phosphoramidite Amine-Exchange Reaction

Journal of Organic Chemistry

Volumn 62, Issue 21, 1997, Pages 7278-7287

  Nelson, Jeffrey S ^a   Fearon, Karen L ^a   Nguyen, Mark Q ^a   McCurdy, Sarah N ^a   Frediani, Jeff E ^a   Foy, Michael F ^a   Hirschbein, Bernard L ^a  

^a ILLUMINA INC   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000965862     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo970801t     Document Type: Article

References (26)

1. Uhlman, E.; Peyman, A. Chem. Rev. 1990, 90, 544.
2. Kibler-Herzog, L.; Zon, G.; Uzanski, B.; Whittier, G.; Wilson, W. D. Nucleic Acids Res. 1991, 19, 2979.
3. (a) Gryaznov, S.; and Chen, J.-K. J. Am. Chem. Soc. 1994, 116, 3143.
4. (b) Chen, J.-K.; Schultz, R. G.; Lloyd, D. H.; Gryaznov, S. M. Nucleic Acids Res. 1995, 23, 2661.
5. (c) Gryaznov, S. M.; Lloyd, D. H.; Chen, J.-K.; Schultz, R. G.; DeDionisio, L. A.; Ratmeyer, L.; Wilson, W. D. Proc. Natl. Acad. Sci. U.S.A. 1995, 92, 5798.
6. McCurdy, S. N.; Nelson, J. S.; Hirschbein, B. L.; Fearon, K. L. Tetrahedron Lett. 1997, 38, 207.
7. The phosphoramidite amine-exchange method has previously been used to form (from one to three) P3′→N5′ phosphoramidate oligonucleotide linkages. (a) Bannwarth, W. Helv. Chim. Acta 1988, 71, 1517. (b) Gryaznov, S. M.; Letsinger, R. L. Nucleic Acids Res. 1992, 20, 3403. The phosphoramidite amine-exchange approach has also been recently described for the synthesis of 2′-fluoro-2′-deoxynucleotide N3′→P5′ phosphoramidates in which the basicity of the 3′-amine is considerably lower than in this reported chemistry where the 2′-position is unfunctionalized. (c) Schultz, R. G.; Gryaznov, S. M. Nucleic Acids Res. 1996, 24, 2966.
8. The phosphoramidite amine-exchange method has previously been used to form (from one to three) P3′→N5′ phosphoramidate oligonucleotide linkages. (a) Bannwarth, W. Helv. Chim. Acta 1988, 71, 1517. (b) Gryaznov, S. M.; Letsinger, R. L. Nucleic Acids Res. 1992, 20, 3403. The phosphoramidite amine-exchange approach has also been recently described for the synthesis of 2′-fluoro-2′-deoxynucleotide N3′→P5′ phosphoramidates in which the basicity of the 3′-amine is considerably lower than in this reported chemistry where the 2′-position is unfunctionalized. (c) Schultz, R. G.; Gryaznov, S. M. Nucleic Acids Res. 1996, 24, 2966.
9. The phosphoramidite amine-exchange method has previously been used to form (from one to three) P3′→N5′ phosphoramidate oligonucleotide linkages. (a) Bannwarth, W. Helv. Chim. Acta 1988, 71, 1517. (b) Gryaznov, S. M.; Letsinger, R. L. Nucleic Acids Res. 1992, 20, 3403. The phosphoramidite amine-exchange approach has also been recently described for the synthesis of 2′-fluoro-2′-deoxynucleotide N3′→P5′ phosphoramidates in which the basicity of the 3′-amine is considerably lower than in this reported chemistry where the 2′-position is unfunctionalized. (c) Schultz, R. G.; Gryaznov, S. M. Nucleic Acids Res. 1996, 24, 2966.
10. Czernecki, S.; Valéry, J.-M. Synthesis 1991, 239.
11. Mikhailopulo, I. A.; Zaitseva, G. V.; Vaaks, E. V.; Rosemeyer, H.; Seela, F. Nucleosides Nucleotides 1992, 11, 273.
12. Chaudhary, S. K.; Hernandez, O. Tetrahedron Lett. 1979, 2, 99.
13. Mitsunobu, O. Synthesis 1981, 1.
14. Reese, C. B.; Skone, P. A. J. Chem. Soc. Perkin Trans. I 1984, 1263.
15. 3N·3HF reagent was found to be acceptable if the reaction is run in dichloromethane/pyridine.
16. (a) Himmelsbach, F.; Schulz, B. S.; Trichtinger, T.; Charubala, R.; Pfleiderer, W. Tetrahedron 1984, 40, 59.
17. (b) Pon, R. T.; Usman, N.; Damha, M. J.; Ogilvie, K. K. Nucleic Acids Res. 1986, 14, 6453.
18. (c) Kamimura, T.; Tsuchiya, M.; Koura, K.; Sekine, M.; Hata, T. Tetrahedron Lett. 1983, 24, 2775.
19. (a) Herdewijn, P. A. M. J. Org. Chem. 1988, 53, 5050.
20. (b) Herdewijn, P.; Van Aerschot, A. Tetrahedron Lett. 1989, 30, 855.
21. 3-O-(Dimethoxytrityl)-2′-deoxynucleoside 5′-(2-cyanoethyl N,N-diisopropylphophoramidites) are available from Glen Research. A 90-s detritylation time with 3% dichloroacetic acid/DCM should be used.
22. Hirschbein, B. L.; et al. Unpublished results.
23. (a) Brill, W. K.-D. Tetrahedron Lett. 1994, 35, 3041.
24. (b) Scremin, C. L.; Zhou, L.; Srinivasachar, K.; Beaucage, S. L. J. Org. Chem. 1994, 59, 1963.
25. 3 with acceptably low levels (≤0.6% ppm) of heavy metals should be utilized.
26. Carpino, L. A.; El-Faham, A.; Minor, C. A.; Albericio, F. J. Chem. Soc., Chem. Commun. 1994, 201 and the references cited therein.