Pyrimidine-Purine and Pyrimidine Heterodinucleosides
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CHARACTERIZATIONS
Spectroscopic data of selected new compounds:
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Compound 4: Rf = 0.52 (AcOEt/EtOH: 9/1); H NMR (DMSO d6): cy-
tidine: 11.22 (s, 1H, NH), 8.31 (br s, 1H, H5), 7.36 (br d, J = 6.8 Hz, H5);
benzoyl: 8.00 (dd, 2H, J = 1.2 Hz, J = 8.5 Hz, H2–6), 7.62 (br t, 1H, J = 7.5 Hz,
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H4), 7.51 (br t, 2H, J = 7.5 Hz, H3–5); ose: 6.13 (t, 1H, J = 6.1 Hz, H1 ), 5.33
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(d, 1H, J = 4.4 Hz, 1H, O3 -H), 4.22 (m, 1H, H3 ), 3.93 (br dd, 1H, J = 3.1
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Hz, J = 11.5 Hz, H5 a), 3.87 (dd, 1H, J = 3.3 Hz, J = 11.5 Hz, H5 b), 2.36 (ddd,
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1H, J = 4.8 Hz, J = 6.1 Hz, J = 13.3 Hz, H2 a), 2.07 (dt, 1H, J = 6.1 Hz, J =
13.3 Hz, H2 b); TBDMS: 0.88 (s, 9H, C-CH3), 0.09 (s, 6H, Si-CH3); 13C NMR
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(DMSO d6): thymine: 162.9 (C4), 154.3 (C2), 144.4 (C6), 95.8 (C5); benzoyl:
167.3 (C O), 133.1 (C1), 132.7 (C4), 128.4 (C2, C3, C5, C6); ose: 87.3 (C4ꢁ),
86.2 (C1ꢁ), 69.6 (C3ꢁ), 62.6 (C5ꢁ), 41.2 (C2ꢁ); TBDMS: 25.7 (C CH3), 17.9
(C CH3a), −5.5 (Si CH3a), −5.6 (Si CH3b).
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Compound 5: Rf = 0.45 (AcOEt/MeOH: 9/1); H NMR (DMSO d6):
cytidine: 11.26 (s, 1H, NH), 8.28 (br s, 1H, H5), 7.36 (br d, J = 7.4 Hz, H5);
benzoyl: 8.01 (dd, 2H, J = 7.2 Hz, J = 1.2 Hz, H2–6), 7.62 (br t, 1H, J = 7.4 Hz,
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H4), 7.51 (br t, 2H, J = 7.6 Hz, H3–5); ose: 6.09 (br t, 1H, J = 6.4 Hz, H1 ),
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4.27 (m, 1H, H3 ), 4.14 (br dd, 1H, J = 3.1 Hz, J = 6.2 Hz, H4 ), 3.87 (br dd,
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1H, J = 3.7 Hz, J = 11.4 Hz, H5 a), 3.78 (br dt, 1H, J = J = 3.3 Hz, 11.4 Hz,
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H5 b), 2.54 (ddd, 1H, J = 3.1 Hz, J = 6.1 Hz, J = 13.3 Hz, H2 a), 2.14 (dt, 1H,
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J = 6.3 Hz, J = 13.3 Hz, H2 b); TBDMS: 0.89 (s, 9H, C CH3), 0.10 (s, 6H,
Si CH3a), 0.09 (s, 6H, Si CH3a); propargyl: 4.23 (br d, 1H, J = 2.3 Hz, J =
18,0 Hz, CH2), 3.47 (t, 1H, J = 2.3 Hz, C H); 13C NMR (DMSO d6): thymine:
163.0 (C4), 154.2 (C2), 144.3 (C6), 95.9 (C5); benzoyl: 167.3 (C O), 133.1
(C1), 132.7 (C4), 128.4 (C2, C3, C5, C6); ose: 86.5 (C1ꢁ), 84.5 (C4ꢁ), 77.7
(C3ꢁ), 62.8 (C5ꢁ), 40.4 (C2ꢁ); TBDMS: 25.7 (C CH3), 17,9 (C CH3), −5.6
(CH3a), −5.6 (CH3b); propargyl: 80.0 (C), 77.4 (CH), 55.9 (CH2); MS (IS)
m/z = 484.4 (MH+), 506.4 (MNa+), 989,7 (M2Na+).
Compound 7: Rf = 0.20 (CHCl3/EtOH: 9/1); 1H NMR (DMSO d6): 11.29
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(s, 2H, NH), 2.52–2.06 (m, 4H, H2 cytidine and thymine); cytidine: 8.28 (d, 1H, J =
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7.4 Hz, H5), 7.34 (d, 1H, J = 7.4, H6); ose: 6.10 (t, 1H, J = 6.4, H1 ), 4.29 (m,
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1H, H3 ), 4.14 (m, 1H, H4 ), 3.85 (dd, 1H, J = 3.5, J = 11.5, H5 ), 3.75 (dd,
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1H, J = 3.2, J = 11.5, H5 ); TBDMS: 0.86 (s, 9H, C (CH3)3), 0.07 (s, 3H,
Si CH3a), 0.06 (s, 3H, Si CH3b); benzoyl: 8.01 (dd, 2H, J = 1.2 Hz, J = 7.4
Hz), 7.62 (br. t, 1H, J = 7.4 Hz), 7.51 (br. t, 2H, J = 7.7 Hz); linker: 8.09 (s, 1H,
Htriazole), 4.57 (d, 2H, J = 12.1, CH2triazole); thymine: 7.35 (s, 1H, H6), 1.80 (s,
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3H, CH3); ose: 6.15 (t, 1H, J = 6.9, H1 ), 5.50 (br. s, 1H, OH), 4.71 (dd, 1H, J =
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4.3 Hz, J = 14.4 Hz, H5 ), 4.70 (dd, 1H, J = 3.4 Hz, J = 14.4 Hz, H5 ), 4.20 (m,
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1H, H3 ), 4.08 (m, 1H, H4 ); C NMR (DMSO d6), 41.4 (C2 cytidine or thymidine),
37.5 (C2ꢁcytidine or thymidine); cytidine: 163.0 (C4), 154.2 (C2), 144.3 (C6), 95.9
(C5); ose: 86.5 (C1ꢁ), 84.9 (C4ꢁ), 78.1 (C3ꢁ); benzoyl: 167.2 (C O), 133.1 (C1),
132.7 (C4), 128.4 (C2, C3, C5, C6); TBDMS: 25.7 (C CH3), 17.9 (C CH3);