Trimethylsilyl triflate → 2-Bromo4,5,6-trichloro-1-(2,3-di-O-acetyl-5-deoxy-beta-D-ribofuranosyl)-1H-benzimidazole

HRID 2227217Notes

Reaction equation

HRID 2227217 reaction equation
[Br:1][C:2]1[NH:6][C:5]2[CH:7]=[C:8]([Cl:13])[C:9]([Cl:12])=[C:10]([Cl:11])[C:4]=2[N:3]=1.C/C(/O[Si](C)(C)C)=N\[Si](C)(C)C.C(O[CH:30]1[O:42][C@H:41]([CH3:43])[C@@H:36]([O:37][C:38](=[O:40])[CH3:39])[C@H:31]1[O:32][C:33](=[O:35])[CH3:34])(=O)C.C[Si](OS(C(F)(F)F)(=O)=O)(C)C>C(#N)C.C(OCC)(=O)C>[Br:1][C:2]1[N:6]([C@@H:30]2[O:42][C@H:41]([CH3:43])[C@@H:36]([O:37][C:38](=[O:40])[CH3:39])[C@H:31]2[O:32][C:33](=[O:35])[CH3:34])[C:5]2[CH:7]=[C:8]([Cl:13])[C:9]([Cl:12])=[C:10]([Cl:11])[C:4]=2[N:3]=1

Participants

7

Reactant 4

HCID 65367Trimethylsilyl triflateHCID 6913588N,O-bis(trimethylsilyl)acetamideHCID 11196237Tri-O-acetyl-5-deoxy-D-ribofuranoseHCID 184219262-Bromo-5,6,7-trichloro-1H-benzimidazole

Product 1

HCID 220862702-Bromo4,5,6-trichloro-1-(2,3-di-O-acetyl-5-deoxy-beta-D-ribofuranosyl)-1H-benzimidazoleYield 58%

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
70 °C

Procedure

2-Bromo4,5,6-trichloro-1H-benzimidazole (0.3 g, 1 mmol), acetonitrile (10 mL), and N,O-bis(trimethylsilyl)acetamide were stirred at 70° C. for 15 min., giving a homogeneous solution. To the solution was then added 1,2,3-tri-O-acetyl-5-deoxyribofuranose (0.31 g, 1.2 mmol) in acetonitrile (5 mL) and trimethylsilyltrifluoromethane sulfonate (0.25 mL, 1.3 mmol). The resulting mixture was allowed to stir at 70° C. for 20 min. The mixture was then allowed to cool to RT and was diluted with ethyl acetate and was washed with a saturated aqueous NaHCO3 solution, dried over NaSO4 and the solvents were removed by rotary evaporation. The product was purified by flash chromatography using chloroform as eluent and then recrystallization from methanol afforded 0.29 g (58%) of the title compound as white crystals; m.p. 160-162° C.; 1H NMR (DMSO-d6) δ: 8.14 (s, 1H), 6.16 (d, 1H), 5.63 (t, 1H), 5.27 (dd, 1H), 4.26 (m, 1H), 2.13 (s, 3H), 2.02 (s, 3H), 1.51 (d, 3H).

Workup

  1. customgiving a homogeneous solution
  2. temperatureto cool to RT
  3. washwas washed with a saturated aqueous NaHCO3 solution
  4. dry with materialdried over NaSO4
  5. customthe solvents were removed by rotary evaporation
  6. customThe product was purified by flash chromatography
  7. customrecrystallization from methanol

Sources & evidence

ORD record
ord-101c212be8864b5e9ee8a8b655983b06
Source dataset
uspto-grants-2002_07
Patent number
US06413938B1

Reaction notes

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