Trimethylsilyl triflate → HCID 10813653, compound

HRID 263881Notes

Reaction equation

HRID 263881 reaction equation
[Cl:1][C:2]1[NH:3][C:4]2[CH:10]=[C:9]([N+:11]([O-:13])=[O:12])[CH:8]=[CH:7][C:5]=2[N:6]=1.C(O[C@@H:18]1[O:30][C@H:29]([CH2:31][O:32][C:33](=[O:35])[CH3:34])[C@@H:24]([O:25][C:26](=[O:28])[CH3:27])[C@H:19]1[O:20][C:21](=[O:23])[CH3:22])(=O)C.[Si](OS(C(F)(F)F)(=O)=O)(C)(C)C>ClCCCl.C(Cl)(Cl)Cl>[Cl:1][C:2]1[N:6]([C@@H:18]2[O:30][C@H:29]([CH2:31][O:32][C:33](=[O:35])[CH3:34])[C@@H:24]([O:25][C:26](=[O:28])[CH3:27])[C@H:19]2[O:20][C:21](=[O:23])[CH3:22])[C:5]2[CH:7]=[CH:8][C:9]([N+:11]([O-:13])=[O:12])=[CH:10][C:4]=2[N:3]=1.[Cl:1][C:2]1[N:3]([C@@H:18]2[O:30][C@H:29]([CH2:31][O:32][C:33](=[O:35])[CH3:34])[C@@H:24]([O:25][C:26](=[O:28])[CH3:27])[C@H:19]2[O:20][C:21](=[O:23])[CH3:22])[C:4]2[CH:10]=[C:9]([N+:11]([O-:13])=[O:12])[CH:8]=[CH:7][C:5]=2[N:6]=1

Participants

7

Reactant 3

HCID 65367Trimethylsilyl triflateHCID 830641,2,3,5-Tetraacetyl-beta-D-ribofuranoseHCID 5160322-Chloro-6-nitro-1H-benzimidazole

Product 2

HCID 10813653HCID 10813653, compoundHCID 10813654HCID 10813654, compound

Reagents, catalysts & solvents 2

HCID 111,2-DichloroethaneSolventHCID 6212ChloroformSolvent

Conditions

Temperature
75 °C

Procedure

To a suspension of 3.952 g (20 mmole) of 19 in 100 mL of 1,2-dichloroethane, was added 5 mL (20 mmole) of BSA. The reaction mixture was stirred at 75° C. for 15 min to give a clear solution. This solution was cooled to ~20° C. and treated with 7.0 g (22 mmole) of 1,2,3,5-tetra-O-acetyl-b-D-ribofuranose and 4.638 mL (24 mmole) of TMSOTf at room temperature for 2 h. The reaction mixture was diluted with 200 mL of CHCl3. The CHCl3 solution was washed with sat. NaHCO3 solution (200 mL×2), sat. NaCl solution (200 mL), dried (Na2SO4), and evaporated. The residue was chromatographed on a silica column (5×35 cm, eluted with CHCl3 and 0.5% MeOH/CHCl3). Evaporation of the appropriate fractions gave 6.50 g (71%. one spot on TLC) of 74 and 75 as a white foam. Fractional recrystallization of this foam (5 times from MeOH) give 1.59 g (17%) of the pure 6-nitro isomer 75. MP 127°-129° C. MS (EI) m/e 455.0750 (2%, M+ =455.0732). 1H NMR (DMSO-d6): d 8.68 (d, 1, 7-H, J7-5 =2.0 Hz), 8.21 (dd, 1, 5-H, J5-4 =9.0 Hz), 7.88 (d, 1, 4-H), 6.41 (d, 1, 1'-H, J1'-2' =7.0 Hz), 5.58 (t, 1, 2'-H, J2'-3' =7.0 Hz), 5.45 (dd, 1, 3'-H, J3'-4' =4.0 Hz), 4.50, 4.40 (2×m, 3, 4'-H and 5'-H), 2.15, 2.12, 2.03 (3×s,9, 3×Ac). 13C NMR (DMSO-d6): d 170.12, 168.49, 169.25 (3×OCOCH3), 145.60 (C3a), 143.96 (C2), 143.65 (C6), 132.45 (C7a), 119.65 (C4), 118.92 (C5), 108.47 (C7), 86.96 (C1'), 79.67 (C4'), 71.12 (C2'), 68.75 (C3'), 62.56 (C5'), 20.39, 20.31, 20.03 (3×OCOCH3).

Workup

  1. additionwas added 5 mL (20 mmole) of BSA
  2. customto give a clear solution
  3. temperatureThis solution was cooled to ~20° C.
  4. washThe CHCl3 solution was washed with sat. NaHCO3 solution (200 mL×2), sat. NaCl solution (200 mL)
  5. dry with materialdried (Na2SO4)
  6. customevaporated
  7. customThe residue was chromatographed on a silica column (5×35 cm, eluted with CHCl3 and 0.5% MeOH/CHCl3)
  8. customEvaporation of the appropriate fractions

Sources & evidence

ORD record
ord-f4adcd5594cb48fcb6cea16791694d9c
Source dataset
uspto-grants-1997_07
Patent number
US05646125

Reaction notes

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