Imidazole → 5'-O-tert-butyldimethylsilyloxy-3'-deoxythymidine

Reaktionsgleichung

[C@@H:1]1([N:8]2[CH:16]=[C:14]([CH3:15])[C:12](=[O:13])[NH:11][C:9]2=[O:10])[O:7][C@H:4]([CH2:5][OH:6])[CH2:3][CH2:2]1.N1C=CN=C1.[Si:22](Cl)([C:25]([CH3:28])([CH3:27])[CH3:26])([CH3:24])[CH3:23].CN(C=[O:34])C>>[Si:22]([O:34][O:6][CH2:5][C@H:4]1[O:7][C@@H:1]([N:8]2[CH:16]=[C:14]([CH3:15])[C:12](=[O:13])[NH:11][C:9]2=[O:10])[CH2:2][CH2:3]1)([C:25]([CH3:28])([CH3:27])[CH3:26])([CH3:24])[CH3:23]

Komponenten

Edukt 4

HCID 795Imidazole

HCID 6228Dimethylformamide

HCID 28928tert-Butyldimethylsilyl chloride

HCID 651192',3'-Dideoxythymidine

Produkt 1

HCID 873648415'-O-tert-butyldimethylsilyloxy-3'-deoxythymidineAusbeute 87 %

Versuchsvorschrift

To a stirred solution of 3′-deoxythymidine (2.0 g, 8.84 mmol) in anhydrous DMF (15 mL) were added imidazole (0.90 g, 13.26 mmol) and tert-butyldimethylsilyl chloride (TBDMSCl) (1.73 g, 11.49 mmol) at r.t., followed by stirring for 4 h. After evaporating the solvent, the residue was partitioned between CH2Cl2 and water. The organic layer was dried over Na2SO4 and evaporated to dryness. The organic residue was purified by silica gel column chromatography with MeOH/CH2Cl2 (0-3%) to give the corresponding product (2.60 g, 7.63 mmol, 87%). 1H NMR (CDCl3, 300 MHz) δ 8.80 (br s, 1H, NH), 7.57 (q, 1H, H6, J=1.2 Hz), 6.07 (dd, 1H, H1′, J=4.8 and 6.3 Hz), 4.10-4.18 (m, 1 H, H4′), 3.98 (dd, 1H, H5′, J=2.4 and 11.4 Hz), 3.70 (dd, 1H, H5′, J=3.0 and 11.4 Hz), 2.30-2.4 (m, 1H, H2′), 1.93-2.04 (m, 3H, H2′ and 2H3′), 1.91 (d, 9H, 3CH3), 0.10 (2s, 6H, 2CH3).