Trimethylsilyl triflate → 2,4,5,6-Tetrachloro-1-(2,3-di-O-acetyl-5-deoxy-beta-D-ribofuranosyl)-1H-benzimidazole

HRID 2227216ノート

反応式

HRID 2227216 の反応式
[Cl: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>[Cl: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

参加物

7

反応物 4

HCID 65367Trimethylsilyl triflateHCID 6913588N,O-bis(trimethylsilyl)acetamideHCID 101989852,4,5,6-tetrachloro-1H-benzimidazoleHCID 11196237Tri-O-acetyl-5-deoxy-D-ribofuranose2 回

生成物 1

HCID 701794282,4,5,6-Tetrachloro-1-(2,3-di-O-acetyl-5-deoxy-beta-D-ribofuranosyl)-1H-benzimidazole収率 61%

試薬・触媒・溶媒 2

HCID 6342Acetonitrile溶媒3 回HCID 8857Ethyl Acetate溶媒

反応条件

温度
70 °C

実験手順

A mixture of 2,4,5,6-tetrachloro-1H-benzimidazole (1.02 g, 4.0 mmol), acetonitrile (20 mL), and N,O-bis(trimethylsilyl)acetamide (1.5 mL, 6 mmol) was stirred at 70° C. for 15 min. Then 1,2,3-tri-O-acetyl-5-deoxy-D-ribofuranose (1.35 g, 5.2 mmol) in acetonitrile (5 mL) was added, followed by trimethylsilyltrifluoromethane sulfonate (1.16 mL, 6.0 mmol). The resulting mixture was allowed to stir at 70° C. for 20 min. Another portion of 1,2,3-tri-O-acetyl-5-deoxy-D-ribofuranose (0.21 g, 0.8 mmol) in acetonitrile (2 mL) was added and stirring was continued at 70° C. for 10 min. The mixture was allowed to cool to RT and was diluted with ethyl acetate. The ethyl acetate layer was washed with a saturated NaHCO3/NaCl solution, dried over Na2SO4 and the solvents were removed by rotary evaporation. The product was purified by flash chromatography using chloroform as eluant. Recrystallization from methanol afforded 1.11 g (61 %) of the title compound as white crystals; m.p. 126-127° C.; 1H NMR (DMSO-d6) δ: 8.16 (s, 1H), 6.20 (d, 1H), 5.61 (t, 1H), 5.25 (dd, 1H), 4.24 (m, 1H), 2.13 (s, 3H), 2.02 (s, 3H), 1.50 (d, 3H).

後処理

  1. stirringto stir at 70° C. for 20 min
  2. stirringstirring
  3. waitwas continued at 70° C. for 10 min
  4. temperatureto cool to RT
  5. washThe ethyl acetate layer was washed with a saturated NaHCO3/NaCl solution
  6. dry with materialdried over Na2SO4
  7. customthe solvents were removed by rotary evaporation
  8. customThe product was purified by flash chromatography
  9. customRecrystallization from methanol

出典と根拠

ORDレコード
ord-5e0c316f4c204fe7a1f47c7df325cc7b
出典データセット
uspto-grants-2002_07
特許番号
US06413938B1

反応ノート

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