Trimethylsilyl triflate → HCID 54258191, compound

HRID 1281678Notes

Reaction equation

HRID 1281678 reaction equation
[F:1][C:2]1[C:10]([F:11])=[CH:9][C:5]2[NH:6][CH:7]=[N:8][C:4]=2[CH:3]=1.C/C(/O[Si](C)(C)C)=N\[Si](C)(C)C.FC(F)(F)S(O[Si](C)(C)C)(=O)=O.C(O[C@@H:40]1[O:57][CH2:56][C@@H:51]([O:52][C:53](=[O:55])[CH3:54])[C@@H:46]([O:47][C:48](=[O:50])[CH3:49])[C@H:41]1[O:42][C:43](=[O:45])[CH3:44])(=O)C.C(=O)(O)[O-].[Na+]>ClCCCl.CO>[F:11][C:10]1[C:2]([F:1])=[CH:3][C:4]2[N:8]([C@@H:56]3[O:57][CH2:40][C@@H:41]([O:42][C:43](=[O:45])[CH3:44])[C@@H:46]([O:47][C:48](=[O:50])[CH3:49])[C@H:51]3[O:52][C:53](=[O:55])[CH3:54])[CH:7]=[N:6][C:5]=2[CH:9]=1

Participants

8

Reactant 5

HCID 65367Trimethylsilyl triflateHCID 97336β-D-Ribopyranose, 1,2,3,4-tetraacetateHCID 3453755,6-DifluorobenzimidazoleHCID 516892Sodium BicarbonateHCID 6913588N,O-bis(trimethylsilyl)acetamide

Product 1

HCID 54258191HCID 54258191, compoundYield 40%

Reagents, catalysts & solvents 2

HCID 111,2-DichloroethaneSolventHCID 887MethanolSolvent

Procedure

As per General Procedure III. 5,6-difluoro-1H-benzimidazole (1.0 g, 6.5 mmol), N,O-bis(trimethlsilyl)acetamide (1.6 ml, 6.5 mmol), in 50 ml 1,2-dichloroethane (Aldrich Sure Seal, Milwaukee) were heated at 85° C. for 2.5 h under a nitrogen atmosphere then allowed to cool to rt. Trimethylsilyl trifluoromethanesulfonate (1.4 ml, 7.2 mmol) and 2.0 g (6.3 mmol) solid 1,2,3,4-tetra-O-acetyl-b-D-ribopyranose (beta-D-ribopyranose 1,2,3,4-tetraacetate, Aldrich, Milwaukee) was added and the mixture was heated in an oil bath at 85° C. for 24 h under a nitrogen atmosphere. The reaction was then poured into 7% aqueous sodium bicarbonate and extracted with dichloromethane. The organic layer was dried with magnesium sulfate (anhyd), filtered, and evaporated. The crude residue was purified on a silica gel column (2.5×20 cm, 230-400 mesh) with CH2Cl2 and an increasing gradient of methanol from 0.5 to 2% to provide the title compound as a white foam (1.1 g, 2.6 mmol, 40%); MS (API+): m/z (rel. intensity) 524 (0.10, M+1); 1H NMR (DMSO-d6) δ8.47 (s,1H), 8.20-8.16 (m, 1H), 7.76-7.71 (m, 1H), 6.02-6.00 (d, 1H, J=9.5 Hz), 5.75-5.69 (m, 2H), 5.53-5.40 (m, 1H), 4.05-3.94 (m, 1H), 2.22 (s, 3H), 2.00 (s, 3H), 1.73 (s, 3H).

Workup

  1. temperaturethe mixture was heated in an oil bath at 85° C. for 24 h under a nitrogen atmosphere
  2. extractionextracted with dichloromethane
  3. dry with materialThe organic layer was dried with magnesium sulfate (anhyd)
  4. filtrationfiltered
  5. customevaporated
  6. customThe crude residue was purified on a silica gel column (2.5×20 cm, 230-400 mesh) with CH2Cl2

Sources & evidence

ORD record
ord-1163147ca1ea4e348e6142019cd4713e
Source dataset
uspto-grants-2002_09
Patent number
US06455507B1

Reaction notes

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