Trimethylsilyl triflate → (1S,3S,4R,7S)-3-(6-N-Benzoyladenin-9-yl)-7-benzyloxy-1-benzyloxymethyl-2,5-dioxabicyclo[2.2.1]heptane

HRID 1663551Notes

Reaction equation

HRID 1663551 reaction equation
C(O[C@H:5]1[C@H:10]2[C@H:11]([O:12][CH2:13][C:14]3[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=3)[C@:7]([CH2:20][O:21][CH2:22][C:23]3[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=3)([CH2:8][O:9]2)[O:6]1)(=O)C.[C:29]([NH:37][C:38]1[N:46]=[CH:45][N:44]=[C:43]2[C:39]=1[NH:40][CH:41]=[N:42]2)(=[O:36])[C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1.O([Si](C)(C)C)S(C(F)(F)F)(=O)=O>C(#N)C>[C:29]([NH:37][C:38]1[N:46]=[CH:45][N:44]=[C:43]2[C:39]=1[N:40]=[CH:41][N:42]2[C@@H:5]1[C@H:10]2[C@H:11]([O:12][CH2:13][C:14]3[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=3)[C@:7]([CH2:20][O:21][CH2:22][C:23]3[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=3)([CH2:8][O:9]2)[O:6]1)(=[O:36])[C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1

Participants

5

Reactant 3

HCID 65367Trimethylsilyl triflateHCID 970756-BenzamidopurineHCID 20610793(1S,3S,4R,7S)-3-Acetoxy-7-benzyloxy-1-benzyloxymethyl-2,5-dioxabicyclo[2.2.1]heptane

Product 1

HCID 20610792(1S,3S,4R,7S)-3-(6-N-Benzoyladenin-9-yl)-7-benzyloxy-1-benzyloxymethyl-2,5-dioxabicyclo[2.2.1]heptaneYield 45.4%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

A solution of furanose 207 (167 mg, 0.434 mmol) and 6-N-benzoyladenine (194 mg, 0.813 mmol) in anhydrous acetonitrile (5.3 mL) was added BSA (0.43 mL, 1.76 mmol) and stirred at room temperature for 1 h. The solution was cooled to 0° C. and trimethylsilyl triflate (0.16 mL, 0.86 mmol) was added dropwise. After stirring at 65° C. for 2 h, the reaction was quenched with a saturated aqueous solution of sodium hydrogen carbonate (40 mL) and the mixture was extracted with dichloromethane (2×50 mL). The combined extract was dried (MgSO4). The solvent was removed under reduced pressure and the residue was purified by chromatography over silica gel with dichloromethane:methanol (98:2) as eluent to give the product 208 as a solid (111 mg, 45%); 1H NMR (CDCl3): δ 8.82 (1 H, s, H-8), 8.14 (1 H, s, H-2), 7.59-7.26 (15 H, m, Bz, Bn), 6.74 (1 H, s, H-1′), 4.92 (1 H, s, H-2′), 4.74-4.39 (4 H, m, Bn), 4.42 (1 H, s, H-3′), 4.19-4.10 (2 H, m, H-5″), 3.92 (1 H, d, J 11.8 Hz, H-5′), 3.88 (1 H, d, J 11.5 Hz, H-5′); MS FAB: 564 (M+H, 100%).

Workup

  1. temperatureThe solution was cooled to 0° C.
  2. stirringAfter stirring at 65° C. for 2 h
  3. customthe reaction was quenched with a saturated aqueous solution of sodium hydrogen carbonate (40 mL)
  4. extractionthe mixture was extracted with dichloromethane (2×50 mL)
  5. extractionThe combined extract
  6. dry with materialwas dried (MgSO4)
  7. customThe solvent was removed under reduced pressure
  8. customthe residue was purified by chromatography over silica gel with dichloromethane:methanol (98:2) as eluent

Sources & evidence

ORD record
ord-86008452b53942189b60a8791be89f42
Source dataset
uspto-grants-2011_10
Patent number
US08034909B2

Reaction notes

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