Hexamethyldisilazane → (5S,2R,3R)-2-(6-chloropurin-9-yl)-5-(phenylcarbonyloxymethyl)oxolan-3-yl acetate

HRID 1373684Notes

Reaction equation

HRID 1373684 reaction equation
S([O-])([O-])(=O)=O.[NH4+].[NH4+].[Cl:8][C:9]1[N:17]=[CH:16][N:15]=[C:14]2[C:10]=1[NH:11][CH:12]=[N:13]2.C[Si](C)(C)N[Si](C)(C)C.C(O[CH:31]1[O:39][C@H:38]([CH2:40][O:41][C:42](=[O:49])[C:43]2[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=2)[CH2:37][C@H:32]1[O:33][C:34](=[O:36])[CH3:35])(=O)C.O([Si](C)(C)C)S(C(F)(F)F)(=O)=O.C(=O)(O)[O-].[Na+]>>[C:34]([O:33][C@@H:32]1[CH2:37][C@@H:38]([CH2:40][O:41][C:42]([C:43]2[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=2)=[O:49])[O:39][C@H:31]1[N:13]1[CH:12]=[N:11][C:10]2[C:14]1=[N:15][CH:16]=[N:17][C:9]=2[Cl:8])(=[O:36])[CH3:35]

Participants

7

Reactant 6

HCID 13838HexamethyldisilazaneHCID 65367Trimethylsilyl triflateHCID 516892Sodium BicarbonateHCID 53592776-ChloropurineHCID 6097028Ammonium SulfateHCID 147571015-O-Benzoyl-1,2-di-O-acetyl-3-deoxy-D-ribofuranose

Product 1

HCID 86594480(5S,2R,3R)-2-(6-chloropurin-9-yl)-5-(phenylcarbonyloxymethyl)oxolan-3-yl acetate

Procedure

A catalytic amount of ammonium sulfate was added to a mixture of 6-chloropurine (0.56 grams, 3.62 mmol) and hexamethyldisilazane (15 mL), and the mixture was refluxed for 3 hours. The solvent was evaporated under reduced pressure, and the residue was co-evaporated with dry toluene (3×10 mL). The white solid residue was dissolved in dry methylene chloride (40 mL) and 1,2-di-O-acetyl-5-O-benzoyl-3-deoxy-ribofuranose, (1.00 g, 3.10 mmol) was added. After 10 minutes of stirring, trimethylsilyl triflate (0.8 mL) was added, and the solution stirred at room temperature for an additional 3 hours. A solution of cold, saturated sodium bicarbonate was added. After 5 minutes stirring, the organic layer was separated and the aqueous solution extracted with methylene chloride (2×30 mL). The organic layers were combined and dried over sodium sulfate, to give (5S,2R,3R)-2-(6-chloropurin-9-yl)-5-(phenylcarbonyloxymethyl)oxolan-3-yl acetate, which was purified by crystallization from methanol. The mother liquor was chromatographed on a Chromatotron, to provide additional product.

Workup

  1. temperaturethe mixture was refluxed for 3 hours
  2. customThe solvent was evaporated under reduced pressure
  3. dissolutionThe white solid residue was dissolved in dry methylene chloride (40 mL)
  4. stirringthe solution stirred at room temperature for an additional 3 hours
  5. stirringAfter 5 minutes stirring
  6. customthe organic layer was separated
  7. extractionthe aqueous solution extracted with methylene chloride (2×30 mL)
  8. dry with materialdried over sodium sulfate

Sources & evidence

ORD record
ord-7550de7047f04cac89c8642409c04c09
Source dataset
uspto-grants-2007_01
Patent number
US07163928B2

Reaction notes

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