Trimethylsilyl triflate → HCID 20610781, compound

HRID 434276Notes

Reaction equation

HRID 434276 reaction equation
[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]

Participants

7

Reactant 5

HCID 65367Trimethylsilyl triflateHCID 516892Sodium BicarbonateHCID 6913588N,O-bis(trimethylsilyl)acetamideHCID 15374265HCID 15374265, compoundHCID 178522337HCID 178522337, compound

Product 1

HCID 20610781HCID 20610781, compound

Reagents, catalysts & solvents 1

HCID 57417360Sodium chloride; waterSolvent

Procedure

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%.

Workup

  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

Sources & evidence

ORD record
ord-f6a511565e614cadb2cf35f7c4ae0ef2
Source dataset
uspto-grants-2003_12
Patent number
US06670461B1

Reaction notes

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