Trimethylsilyl triflate → 1-(2-O-Acetyl-4-C-acetoxymethyl-3,5-di-O-benzyl-beta-D-ribofuranosyl)-4-N-benzoylcytosine

HRID 659857Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 659857
[C:1]([O:4][CH2:5][C@:6]1([CH2:27][O:28][CH2:29][C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)[O:14][CH:9](OC(=O)C)[C@H:8]([O:15][C:16](=[O:18])[CH3:17])[C@@H:7]1[O:19][CH2:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)(=[O:3])[CH3:2].[C:36]([NH:44][C:45]1[CH:50]=[CH:49][NH:48][C:47](=[O:51])[N:46]=1)(=[O:43])[C:37]1[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1.C/C(/O[Si](C)(C)C)=N\[Si](C)(C)C.O([Si](C)(C)C)S(C(F)(F)F)(=O)=O.C(=O)([O-])O.[Na+]>[Cl-].[Na+].O>[C:16]([O:15][C@@H:8]1[C@H:7]([O:19][CH2:20][C:21]2[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=2)[C@@:6]([CH2:5][O:4][C:1](=[O:3])[CH3:2])([CH2:27][O:28][CH2:29][C:30]2[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=2)[O:14][C@H:9]1[N:48]1[CH:49]=[CH:50][C:45]([NH:44][C:36](=[O:43])[C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)=[N:46][C:47]1=[O:51])(=[O:18])[CH3:17]

Komponenten

7

Edukt 5

HCID 65367Trimethylsilyl triflateHCID 516892Sodium BicarbonateHCID 6913588N,O-bis(trimethylsilyl)acetamideHCID 153742654-C-(Acetoxymethyl)-1,2-di-O-acetyl-3,5-di-O-benzyl-D-ribofuranoseHCID 178522337HCID 178522337, Verbindung

Produkt 1

HCID 206107811-(2-O-Acetyl-4-C-acetoxymethyl-3,5-di-O-benzyl-beta-D-ribofuranosyl)-4-N-benzoylcytosine

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 57417360Sodium chloride; waterLösungsmittel

Versuchsvorschrift

To a stirred solution of the anomeric mixture 33 (4.0 g, 8.22 mmol) and 4-N-benzoylcytosine (2.79 g, 13.0 mmol) was added N,O-bis(trimethylsilyl)acetamide (8.16 cm3, 33.0 mmol). The reaction mixture was stirred for 1 h at room temperature and cooled to 0° C. Trimethylsilyl triflate (3.0 cm3, 16.2 mmol) was added dropwise and the mixture was stirred at 60° C. for 2 h. Saturated aqueous solutions of sodium hydrogencarbonate (3×20 cm3) and brine (2×20 cm3) were successively added, and the separated organic phase was dried (Na2SO4). The solvent was removed under reduced pressure and the residue was purified by silica gel column chromatography using dichloromethane/methanol (99:1, v/v) as eluent to give compound 54 as a white solid material (3.9 g, 74%). δH (CDCl3), 8.28 (1H, d, J 7.5, 6-H), 7.94-7.90 (2H, m, Bz), 7.65-7.25 (13H, m, Bn, Bz), 7.16 (1H, d, J 7.1, 5-H), 6.22 (1H, d, J 2.8, 1′-H), 5.51 (1H, dd, J 2.8, 5.8, 2′-H), 4.62 (1H, d, J 11.6, Bn), 4.51 (1H, d, J 12.3, 1″-Ha), 4.49-4.34 (4H, m, 3′-H, Bn), 4.21 (1H, d, J 12.3, 1″-Hb), 3.85 (1H, d, J 10.3, 5′-Ha), 3.47 (1H, d, J 10.3, 5′-Hb), 2.13 (3H, s, COCH3), 2.06 (3H, s, COCH3). δC (CDCl3) 170.52, 169.61 (C═O), 166.83, 162.27 (C-4, C═O), 154.26 (C-2), 145.26 (C-6), 137.25, 136.93, 133.18, 129.0, 128.75, 128.51, 128.45, 128.18, 128.10, 127.89, 127.71 (Bn, Bz), 96.58 (C-5), 89.42, 86.52 (C-1′, C-4′), 76.21, 75.10, 74.17, 73.70, 69.70, 63.97 (C-2′, C-3′, Bn, C-5′, C-1″), 20.82 (COCH3). FAB-MS m/z 664 [M+Na]+, 642 [M+H]+. Found: C, 65.0; H, 5.7; N, 6.5; C35H35N3O9 requires C, 65.5; H, 5.5; N, 6.5%.

Aufarbeitung

  1. temperaturecooled to 0° C
  2. stirringthe mixture was stirred at 60° C. for 2 h
  3. dry with materialthe separated organic phase was dried (Na2SO4)
  4. customThe solvent was removed under reduced pressure
  5. customthe residue was purified by silica gel column chromatography

Quellen und Nachweise

ORD-Eintrag
ord-7fdb9656634b4edda4f08826814dfc01
Quelldatensatz
uspto-grants-2011_12
Patentnummer
US08080644B2

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