A High Field NMR Study of 2′-Deoxyribo-C-Nucleosides

References

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• The details of the synthetic steps and the biophysical studies related to these compounds will be published elsewhere
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• Among proposed methods are the comparison of the chemical shifts of the diastereotopic protons on C2 11, the comparison of the 13C chemical shifts of C4; and C5 12, and the NOE observed on the protons of the sugar ring13
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• Reagents and procedures: from 1 to 2: i, diphenylcadmium; ii, preparative TLC on silica, ethyl acetate/petroleum ether (1:15. v/v); Rf, 2a 0.23, 2b. 0, 20. From 1 to 4:, i, excess penten-4-yl-magnesium bromide; ii, ozone, -78′c, HC1 in methanol (1M): iii, conc. ammonia; iv, DMTrCI, pyridine; v, preparative TLC on silica, methylene chloride/methanol (95:5, v/v + 1% triethylamine): 5 successive elutions on the same plate; 4a, front, 4b, queue. From 5 to 2b:, i, 1, 3-dichloro-1, 1, 3, 3-tetraisopropyldisiloxane; ii, phenylchlorothionocarbonate; iii AIBN/n-Bu3SnH; iv, (Bu)4N+F-; v, p-chlorobenzoylchloride
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• in CDC13, on a Bruker AM 500 NMR spectrometer DeIta TMS (ppm): 2a, 2.35 (H2″), 2.90 (H2′), 4.58 (2H5). 4.67 (H4), 5.38 (H1), 5.58 (H3), 7.25 to 7.38 (5H. phenyl), 7.41 (4H), 7.64 (2H) and 8.01 (2H) (p-chlorobenzoyl), 2b, 2.23 (H2′), 2.55 (H2″), 4.53 (H4), 4.66 (2H5). 5.26 (HI), 5.60 (H3), 7.24 to 7.46 (5H, phenyl), 7.35 (4H). 7.95 (2H) and 8 02 (2H) (p-chlorobenzoyl); the coupling constants of interest for 2a, and 2b, are reported in Table I. 4a, 1.65 (H2″ and 2H6), 1.75 (2H7), 2.28 (2Hg), 2.35 (H2′), 3.09 and 3.27 (2H5). 3.95 (H4), 4.05 (HI), 4.27 (H3); JH-H (Hz): 1–2′, 6.5; 2′-3, 6.5: 3–4, 5.0: 4b, 1.62 (2H6). 1.74 (H2′ and 2H7), 1.94 (H2″), 2.26 (2H8), 3:08 and 3.20 (2H5), 3.91 (H4), 4.16 (H1-). 4.27 (H3); JH-H (Hz):1–2′, 9.8;1–2″, 5.5; 2–3, 6.3; 2″-3, 2.2; 3–4, 2.5
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