Trimethylsilyl triflate → [(2R,3R,4R,5R)-3,4-diacetoxy-5-(2-bromo-5,6-dichloro-benzimidazol-1-yl)tetrahydrofuran-2-yl]methyl acetate

HRID 727002

反応式

HRID 727002 の反応式
[Br:1][C:2]1[NH:3][C:4]2[CH:10]=[C:9]([Cl:11])[C:8]([Cl:12])=[CH:7][C:5]=2[N:6]=1.ClC1C(Cl)=CC2=NC(=O)N=C2C=1.C(O[C@@H:29]1[O:41][C@H:40]([CH2:42][O:43][C:44](=[O:46])[CH3:45])[C@@H:35]([O:36][C:37](=[O:39])[CH3:38])[C@H:30]1[O:31][C:32](=[O:34])[CH3:33])(=O)C.[Si](OS(C(F)(F)F)(=O)=O)(C)(C)C>CC#N.CCOC(C)=O>[Br:1][C:2]1[N:3]([C@@H:29]2[O:41][C@H:40]([CH2:42][O:43][C:44](=[O:46])[CH3:45])[C@@H:35]([O:36][C:37](=[O:39])[CH3:38])[C@H:30]2[O:31][C:32](=[O:34])[CH3:33])[C:4]2[CH:10]=[C:9]([Cl:11])[C:8]([Cl:12])=[CH:7][C:5]=2[N:6]=1

参加物

7

反応物 4

HCID 65367Trimethylsilyl triflateHCID 830641,2,3,5-Tetraacetyl-beta-D-ribofuranoseHCID 4660172-bromo-5,6-dichloro-1H-benzimidazoleHCID 219664025,6-Dichlorobenzimidazol-2-one

生成物 1

HCID 466020[(2R,3R,4R,5R)-3,4-diacetoxy-5-(2-bromo-5,6-dichloro-benzimidazol-1-yl)tetrahydrofuran-2-yl]methyl acetate

試薬・触媒・溶媒 2

HCID 6342Acetonitrile溶媒HCID 8857Ethyl Acetate溶媒

実験手順

To a suspension of (7) (47.867 g, 180 mmol) in 540 mL of dry MeCN, was added 45 mL (180 mmol) of BSA. The reaction mixture was stirred at room temperature for 15 min to give a clear solution. A small amount of solid impurity remained unsilylated, believed to be 5,6-dichlorobenzimidazol-2-one from the starting material(7). 1,2,3,5-Tetra-O-acetyl-β-D-ribofuranose (60.14 g, 189 mmole) was added to this solution and then TMSOTf (38.267 mL 198 mmol) was added dropwise over 20 min. After the addition had been completed, stirring was continued at room temperature for 30 min. The reaction mixture was diluted with 2 L of EtOAc. The EtOAc solution was washed with 1:1 saturated aquenous NaHCO3 /saturated aquenous NaCl (1.5 L×2), dried (Na2SO4, 100 g), decolorized (activated charcoal, 6 g), and filtered through Celite. The filtrate was evaporated and the residue was recrystallized from MeOH to give 82.21 g (4 crops, 87%) of 52a as white needles. MP: 140°-144° C. This product was pure by 1H NMR.

後処理

  1. additionwas added 45 mL (180 mmol) of BSA
  2. customto give a clear solution
  3. additionAfter the addition
  4. stirringstirring
  5. waitwas continued at room temperature for 30 min
  6. washThe EtOAc solution was washed with 1:1 saturated aquenous NaHCO3 /saturated aquenous NaCl (1.5 L×2)
  7. dry with materialdried (Na2SO4, 100 g)
  8. filtrationfiltered through Celite
  9. customThe filtrate was evaporated
  10. customthe residue was recrystallized from MeOH

出典と根拠

ORDレコード
ord-1bb4eecffefe4020a792294a849a3ed3
出典データセット
uspto-grants-1998_01
特許番号
US05712255

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