Trimethylsilyl triflate → 4-Chloro-1-(2,3,5-tri-O-benzoyl-beta-D-ribofuranosyl)pyrimidin-2-one

HRID 1107648Notes

Reaction equation

HRID 1107648 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]([O:8]CC[Si](C)(C)C)[N:3]=1.C(O[CH:19]1[O:41][C@H:40]([CH2:42][O:43][C:44](=[O:51])[C:45]2[CH:50]=[CH:49][CH:48]=[CH:47][CH:46]=2)[C@@H:30]([O:31][C:32](=[O:39])[C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)[C@H:20]1[O:21][C:22](=[O:29])[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)(=O)C.[Si](OS(C(F)(F)F)(=O)=O)(C)(C)C>C(#N)C.C(Cl)Cl>[Cl:1][C:2]1[CH:7]=[CH:6][N:5]([C@@H:19]2[O:41][C@H:40]([CH2:42][O:43][C:44](=[O:51])[C:45]3[CH:50]=[CH:49][CH:48]=[CH:47][CH:46]=3)[C@@H:30]([O:31][C:32](=[O:39])[C:33]3[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=3)[C@H:20]2[O:21][C:22](=[O:29])[C:23]2[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=2)[C:4](=[O:8])[N:3]=1

Participants

6

Reactant 3

HCID 65367Trimethylsilyl triflateHCID 102632784-Chloro-2-(2-trimethylsilanyl-ethoxy)-pyrimidineHCID 109292421-O-Acetyl-2,3,5-tri-O-benzoyl-D-ribofuranose

Product 1

HCID 102575224-Chloro-1-(2,3,5-tri-O-benzoyl-beta-D-ribofuranosyl)pyrimidin-2-one

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of 12 (8.17 g. 35.4 mmol) in 200 mL anhydrous acetonitrile is treated with 1-O-acetyl-2,3,5-tri-O-benzoyl-D-ribofuranose (Pfanstiehl) at room temperature and under an atmosphere of argon. To this mixture is added TMS-triflate (6.11 mL, 35.4 mmol) and the mixture stirred at this temperature for 2 hr. Evaporation of the solvents in vacuo yielded an amber syrup which was immediately redissolved in 300 mL CH2Cl2, washed with cold, saturated NaHCO3 (2×150 mL), dried over magnesium sulfate, filtered and evaporated to a tan residue. Trituration of this residue with cold, anhydrous acetonitrile yielded analytically pure 13, 14.4 g (71%). 1H-NMR (DMSO-d6): δ 8.39 (d, 1 H, 6-H, J6,5 =11.8 Hz); 8.0-7.4 (m, 15 H, aromatic); 6.68 (d, 1 H, H-5); 6.11 (d, 1H, H-1', J1,2=2 Hz); 5.95 (m, 2 H, H-2',3'); 4.85 (m, 1 H, H-4'); 4.70 (m, 2 H, H-5',5"). Anal. Calcd for C30H23N2O8Cl: C, 62.67; H, 4.03; N, 4.87. Found: C, 62.21; H, 3.92; N, 4.80.

Workup

  1. customEvaporation of the solvents in vacuo
  2. customyielded an amber syrup which
  3. washwashed with cold, saturated NaHCO3 (2×150 mL)
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. customevaporated to a tan residue
  7. customTrituration of this residue with cold, anhydrous acetonitrile yielded analytically pure 13, 14.4 g (71%)

Sources & evidence

ORD record
ord-3def2b9048e94060856f4c70eec06203
Source dataset
uspto-grants-2000_05
Patent number
US06060592

Reaction notes

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