Trimethylsilyl triflate → HCID 178476610, compound

HRID 989428Notes

Reaction equation

HRID 989428 reaction equation
[C:1]([NH:9][C:10]1[N:18]=[CH:17][N:16]=[C:15]2[C:11]=1[NH:12][CH:13]=[N:14]2)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(O[CH:23]1[O:39][C:38]([CH2:46][O:47][S:48]([CH3:51])(=[O:50])=[O:49])([CH2:40][O:41][S:42]([CH3:45])(=[O:44])=[O:43])[C@@H:29]([O:30][CH2:31][C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)[C@H:24]1[O:25][C:26](=[O:28])[CH3:27])(=O)C.[Si](OS(C(F)(F)F)(=O)=O)(C)(C)C.C([O-])(O)=O.[Na+]>C(#N)C>[C:26]([O:25][C@@H:24]1[C@H:29]([O:30][CH2:31][C:32]2[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=2)[C:38]([CH2:46][O:47][S:48]([CH3:51])(=[O:50])=[O:49])([CH2:40][O:41][S:42]([CH3:45])(=[O:43])=[O:44])[O:39][C@H:23]1[N:18]1[C:10]([NH:9][C:1](=[O:8])[C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)=[C:11]2[C:15](=[N:14][CH:13]=[N:12]2)[N:16]=[CH:17]1)(=[O:28])[CH3:27]

Participants

6

Reactant 4

HCID 65367Trimethylsilyl triflateHCID 970756-BenzamidopurineHCID 516892Sodium BicarbonateHCID 10973257D-erythro-Pentofuranose, 4-C-[[(methylsulfonyl)oxy]methyl]-3-O-(phenylmethyl)-, 1,2-diacetate 5-methanesulfonate

Product 1

HCID 178476610HCID 178476610, compoundYield 68%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

6-N-Benzoyladenine (11.02 g.; 46.1 mmol) was dried in vacuo overnight. 1,2-Di-O-acetyl-3-O-benzyl-4-C-methanesulfonyloxymethyl-5-O-methanesulfonyl-D-ribofuranose (19.6 g.; 38.4 mmol) (3) was coevaporated in anh. acetonitrile (3×50 mL) and dried in vacuo overnight. 3 was redissolved in anh. 1,2-dichloroethane (stored over molecular sieves) (175 mL), 6-N-Benzoyladenine was added followed by N,O-bistrimethylsilylacetamide (25.1 mL; 101.3 mmol). The mixture was refluxed for 1 h and cooled to rt. TMS-triflate (13.9 mL; 76.8 mmol) was added and the mixture was refluxed for 5h, stirred overnight at rt, refluxed for further 24 h (red-brown solution) and cooled to rt. The solution was poured into an ice-cold saturated aqueous solution of NaHCO3 (200 mL) and stirred for 0.5 h. The precipitate was filtered off, the phases were separated and the organic phase was washed with a saturated aqueous solution. of NaHCO3 (3×150 mL), dried (Na2SO4) and evaporated. Purification by silica gel column chromatography (1-1.5% MeOH in CH2Cl2) gave 4D as a slightly yellow solid in 68% yield (18.0 g.). NMR was consistent with the data reported in an earlier patent.

Workup

  1. customdried in vacuo overnight
  2. dissolution3 was redissolved in anh. 1,2-dichloroethane (stored over molecular sieves) (175 mL)
  3. addition6-N-Benzoyladenine was added
  4. temperatureThe mixture was refluxed for 1 h
  5. temperaturerefluxed for further 24 h (red-brown solution)
  6. temperaturecooled to rt
  7. stirringstirred for 0.5 h
  8. filtrationThe precipitate was filtered off
  9. customthe phases were separated
  10. washthe organic phase was washed with a saturated aqueous solution
  11. dry with materialof NaHCO3 (3×150 mL), dried (Na2SO4)
  12. customevaporated
  13. customPurification by silica gel column chromatography (1-1.5% MeOH in CH2Cl2)

Sources & evidence

ORD record
ord-4321edcf3d7643b2b9f1eb9245ea8f64
Source dataset
uspto-grants-2003_10
Patent number
US06639059B1

Reaction notes

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