An Improved Method for The Preparation Of The Phosphoramidites Of Modified 2′-Deoxynucleotides: Incorporation Of 8-Oxo-2′-Deoxy-7H-Guanosine Into Synthetic Oligomers

References

• Strictly speaking these compounds should be named as purine nucleoside derivatives. However, for convenience in referring to them we have elected to use the 8–0×0–2′-deoxy-7H-guanosine terminology
   Google Scholar
• Kasai , H. and Nishimura , S. 1984 . Nucleic Acids Res. , 12 : 2137
   PubMed Web of Science ®Google Scholar
• Kasai , H. and Nishimura , S. 1984 . Gann , 75 : 565
   PubMedGoogle Scholar
• Kasai , H. and Nishimura , S. 1984 . Gann , 75 : 841
   PubMedGoogle Scholar
• Kasai , H. , Tanooka , H. and Nishimura , S. 1984 . Gann , 75 : 1037
   PubMedGoogle Scholar
• Kasai , H. , Crain , P. F. , Kuchino , Y. , Nishimura , S. , Ootsuyama , A. and Tanooka , H. 1986 . Carcinogenesis , 7 : 1849
   PubMed Web of Science ®Google Scholar
• Kuchino , Y. , Mori , F. , Kasai , H. , Inoue , H. , Iwai , S. , Miura , K. , Ohtsuka , E. and Nishimura , S. 1987 . Nature , 327 : 77
   PubMed Web of Science ®Google Scholar
• Jones , D. S. , Nemoto , F. , Kuchino , Y. , Ohtsuka , E. and Nishimura , S. 1990 . Nucleosides and Nucfeotides , 9 : 223
   Web of Science ®Google Scholar
• Lin , T-S. , Cheng , J-C. , Ishiguro , K. and Sartorelli , A. C. J. 1985 . Med. Chem. , 28 : 1194
   Google Scholar
• Holmes , R. E. and Robins , R. K. 1965 . J. Am. Chem. Soc. , 87 : 1772
   PubMed Web of Science ®Google Scholar
• Ti , G. S. , Gaffney , B. L. and Jones , R. A. J. 1982 . Am. Chem. Soc. , 104 : 1316
   Web of Science ®Google Scholar
• Schaller , H. , Weimann , G. , Lerch , B. and Khorana , H. G. J. 1963 . Am. Chem. Soc. , 85 : 3821
   Web of Science ®Google Scholar
• Smith , M. , Rammler , D. H. , Goldberg , I. H. and Khorana , H. G. 1962 . J. Am. Chem. Soc. , 84 : 430
   Web of Science ®Google Scholar
• Compound 6, like many of the 5′-O-DMT-2′-deoxynucleosides that we have synthesized appears to retain water tenaciously (perhaps as a partial hydrate) and needs rigorous drying before phosphoramidite preparation is attempted
   Google Scholar
• Karpyshev , N. N. 1988 . Russian Chemical Reviews , 57 : 886
   Google Scholar
• Sinha , N. D. , Biernat , J. , McManus , J. and Koster , H. 1984 . Nucleic Acids Res. , 12 : 4539
   PubMed Web of Science ®Google Scholar
• Sinha , N. D. , Biernat , J. and Koster , H. 1983 . Tetrahedron Letters , 24 : 5843
   Web of Science ®Google Scholar
• McBride , L. J. and Caruthers , M. H. 1983 . Tetrahedron Letters , 24 : 245
   Web of Science ®Google Scholar
• Beaucage , S. L. and Caruthers , M. H. 1981 . Tetrahedron Letters , 22 : 1859
   Web of Science ®Google Scholar
• By 31P NMR analysis, the most significant contaminant appears to be a hydrolysis product of the phosphite reagent
   Google Scholar
• Barone , A. D. , Tang , J-Y. and Caruthers , M. H. 1984 . Nucleic Acids Res. , 12 : 4051
   PubMed Web of Science ®Google Scholar
• Satisfactory physical data were obtained for all new substances described in this paper. Data for representative products are as follows. 4. TLC (CH2 Cl2/MeOH 4:1): Rf 0. 72; m. p. 220° C; UV (MeOH): 293, 258; 1H NMR (300 MHz, DMSO-d6) [sgrave] 12. 03 (1H, NH, s), 11. 52 (1H, NH, s), 7.52–7. 31 (5H, aryl, m), 6. 17 (1H, H-C(l′), t, J = 7. 05 Hz), 5. 48 (2H, -CH2 -Ph, s), 5.20 (1H, HO-C(3′-), d, J = 3.90 Hz), 4.70 (1H, HO-C(5′), t, J = 5.55 Hz), 4. 26 (1H, H-C(3′-), m), 3.72 (1H, H-C(4′), m), 3.44 - 3.38 (2H, H-C(5′), m), 2.90 (1H, H-C(2′-), m), 2.76 (1H, -CH-CO-N, m), 2.06 (1H, H-C(2′-), m), 1.12 (6H, C-(Me)2, d, J = 6.90 Hz). 13C NMR (75 MHz, DMSO-d6) [sgrave] 180.67, 154.56, 153.29, 148.43, 147.84, 136.35, 129.31, 129.22, 129.07, 115.79, 88.20, 82.57, 71.98, 71.58, 62.78, 36.88, 35.53, 19.69. FAB/MS (+ ve ion, thioglycerol matrix): m/z 444 [(M + H)+, 7%], 328 [(Heterocyclic base + 2H)+, 9%], 274 (17%), 232 (51%), 181 (44%). (5) TLC (CH2Cl2/MeOH 4:1): Rf 0.56; m. p. 230° C (dec.); UV (MeOH): 301, 265; 1H NMR (300 MHz, DMSO-d6) [sgrave] 12.14 (1H, NH, s), 11.59 (1H, NH, s), 11.28 (1H, NH, s), 6.09 (1H, H-C(1′), t, J = 6.60 Hz), 5.17 (1H, HO-C(3′-), d, J = 2.40 Hz), 4.73 (1H, HO-C(5′), m), 4.37 (1H, H-C(3′-), m), 3.75 (1H, H-C(4′), m), 3.59–3.44 (2H, H-C(5′), m), 3.07 (1H, H-C(2′-), m), 2.74 (1H-CH-CO-N, m), 1.98 (1H, H-C(2′-), m), 1.11 (6H, C-(Me)2, d, J = 8.10 Hz). FAB/MS (+ve ion, thioglycerol matrix): m/z 354 [(M + H)+, 8%], 238 [(Heterocyclic base+2H)+. 15%]. (6) TLC (CH2Cl2/MeOH 4:1): Rf 0.78; m. p. 164 - 166°C; UV (MeOH): 302, 265, 201; 1H NMR (300 MHz, DMSO-d), [sgrave] 12.13 (1H, NH, s), 11.43 (1H, NH, s), 11.24 (1H, NH, s), 7.34 - 6.76 (13H, aryl, m), 6.14 (1H, H-C(1′), t, J = 6.05 Hz), 5.16 (1H, HO-C(3′-), d, J = 4.50 Hz), 4.44 (1H, H-C(3′-), m), 3.91 (1H, H-C(′), m), 3.72 and 3.71 (6H, OCH3, a), 3.32 and 3.06 (2H, H-C(5′), h), 2.98 (1H, H-C(2′-), m), 2.74 (1H, -CH-CO-N, m), 2.12 (1H, H-C(2′-), m), 1.12 (6H, C-(Me)2, d, J = 6.60 Hz). FAB/MS (-ve ion, thioglycerol matrix): m/z 654 [(M-H)−, loo%], 584 (28%), 352 (12%), 236 [(Heterocyclic base-H)−, 30961. (7) TLC (CH2CI2/MeOH 8:1): Rf 0.73; 1H NMR (300 MHz, CDCl3): two diastereomers, [sgrave] 11.75 -11.13 (3H, 3NH, br s), 7.34 - 6.73 (13H, aryl, m), 6.12 (1H, H-C(1′), 2t, two diastereomers), 4.61 (1H, H-C(3′-), m), 4.03 (3H, H-C(4′) and -O-CH2-C, m), 3.71 (6H, OCH3, s), 3.45 (2H, -N-CH(iPr)2, m), 3.34 - 3.92 (2H, H-C(5′), m), 2.76 (2H, -CH2-CN, t, J = 6.0 Hz), 2.63 (1H, -CH-CO-N, m), 2.31 (2H, H-C(2′-), m), 1.26 (12H, -CH3 of (iPr)2, dd), 1.15 (6H, -CO-C(Me)2, dd). 31P NMR (121 MHz, CDC13) [sgrave] 146.63, 146.50 (two diastereomers). FAB/MS (-ve ion, thioglycerol matrix): m/z 854 [(M-H)−, 12%], 654 (14%, loss of phosphoramidite), 236 [(Heterocyclic base-H)−, 7%]
   Google Scholar
• Takeshita , M. , Chang , C-N. , Johnson , F. , Will , S. and Grollman , A. P. 1987 . J. Biol. Chem. , 262 : 10171
   PubMed Web of Science ®Google Scholar
• Millican , T. A. , Mock , G. A. , Chauncey , M. A. , Patel , T. P. , Eaton , M. A. W. , Gunning , J. , Cutbush , S. D. , Neidle , S. and Mann , J. 1984 . Nucleic Acids Res. , 12 : 7435
   PubMed Web of Science ®Google Scholar
• Takeshita , M. , Peden , K. W. C. , Cheng , C.-N. , Will , S. G. , Johnson , F. and Grollman , A. P. 1986 . J. Environ. Mut. Soc. , 8 : 84
   Google Scholar
• Eritja , R. , Walker , PA , Randall , S. K. , Goodman , M. F. and Kaplan , B. E. 1987 . Nucleosides and Nucleotides , 6 : 803
   Google Scholar
• Marinelli , E. R. , Johnson , F. , Iden , C. R. and Yu , P-L. 1990 . Chem. Res. Toxicol. , 3 : 49
   PubMedGoogle Scholar
• Shibutani , S. , Gentles , R. G. , Iden , C. R. and Johnson , F. J. 1990 . Am. Chem. Soc. , 112 : 5667
   Web of Science ®Google Scholar