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A High-field Nmr-study of 2'-deoxyribo-c-nucleosides

Bibliographic reference François, Pierre ; Sonveaux, Etienne ; Touillaux, Roland. A High-field Nmr-study of 2'-deoxyribo-c-nucleosides.INTERNATIONAL SYMP ON THE ANALYSIS OF NUCLEOSIDE, NUCLEOTIDE AND OLIGONUCLEOTIDE COMPOUNDS (UNIV ANTWERP, ANTWERP (Belgium), Sep 19-22, 1989). In: Nucleosides and Nucleotides, Vol. 9, no. 3, p. 379-382 (1990)
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  1. Millican T.A., Mock G.A., Chauncey M.A., Patel T.P., Eaton M.A.W., Gunning J., Cutbush S.D., Neidle S., Mann J., Synthesis and biophysical studies of short oligodeoxynudeotides with novel modifications: a possible approach to the problem of mixed base oligodeoxynudeotide synthesis, 10.1093/nar/12.19.7435
  2. The details of the synthetic steps and the biophysical studies related to these compounds will be published elsewhere
  3. Among proposed methods are the comparison of the chemical shifts of the diastereotopic protons on C211, the comparison of the 13Cchemical shifts of C4; and C512, and the NOE observed on the protons of the sugar ring13
  4. Reagents and procedures:from 1 to 2: i, diphenylcadmium; ii, preparative TLC on silica, ethyl acetate/petroleum ether (1:15. v/v); Rf,2a0.23,2b. 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
  5. Gunning J., Neidle S., Millican T. A., Eaton M. A. W., Mock G. A., Mann J., The structure of 3,5-di-O-benzoyl-1,2-dideoxy-1-phenyl-β-D-ribofuranose, C25H22O5, 10.1107/s010827018500525x
  6. Fox J. J., Klein R. S., Kotick M. P., Watanabe K. A., Nucleosides. LXXIII. Ribosyl analogs of chloramphenicol, 10.1021/jo00825a022
  7. 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 for2a, and2b, 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
  8. Haasnoot C. A. G., de Leeuw F. A. A. M., de Leeuw H. P. M., Altona C., The relationship between proton-proton NMR coupling constants and substituent electronegativities. II—conformational analysis of the sugar ring in nucleosides and nucleotides in solution using a generalized Karplus equation, 10.1002/mrc.1270150111
  9. Raap J., Van Boom J. H., Van Lieshout H. C., Haasnoot C. A. G., Conformations of methyl 2'-deoxy-.alpha.-D-ribofuranoside and methyl 2'-deoxy-.beta.-D-ribofuranoside. A proton magnetic resonance spectroscopy and molecular mechanics study, 10.1021/ja00217a007
  10. Ford K. G., Neidle S., Eaton M. A. W., Millican T. A., Mann J., Structure of 1,2-dideoxy-1-(3-pyridyl)-α-D-ribofuranose, 10.1107/s0108270187089340
  11. With, for the N form, P=0; φm=35, and for the S form, P=180, φ m=35
  12. Srivastava Prem C., Robbins Roland K., Takusagawa F., Berman H. M., Determination of the anomeric configuration of 2′-deoxy-D-ribonucleosides by1H NMR and by crystallographic studies of a novel 2′-deoxyC-nucleoside, 10.1002/jhet.5570180838
  13. Hacksell Uli, Cheng Jane Chi-Ya, Daves G. Doyle, 1H and13C NMR Spectroscopy of Stereoisomeric 2′-deoxy-C-Nucleosides, 10.1080/07328308608062967
  14. Knutsen Lars J. S., Judkins Brian D., Newton Roger F., Scopes David I. C., Klinkert Graham, Synthesis of imidazo-fused bridgehead-nitrogen 2′-deoxyribo-C-nucleosides: coupling-elimination reactions of 2,5-anhydro-3,4,6-tri-O-benzoyl-D-allonic acid, 10.1039/p19850000621