Sodium Thiosulfate → (3aR,4R,6R,6aR)-6-(6-Chloro-9H-purin-9-yl)-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxol-4-carbaldehyde

HRID 552705Notes

Reaction equation

HRID 552705 reaction equation
CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.[Cl:23][C:24]1[N:32]=[CH:31][N:30]=[C:29]2[C:25]=1[N:26]=[CH:27][N:28]2[C@H:33]1[C@@H:37]2[O:38][C:39]([CH3:42])([CH3:41])[O:40][C@@H:36]2[C@@H:35]([CH2:43][OH:44])[O:34]1.S([O-])([O-])(=O)=S.[Na+].[Na+]>C(Cl)Cl.CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O>[Cl:23][C:24]1[N:32]=[CH:31][N:30]=[C:29]2[C:25]=1[N:26]=[CH:27][N:28]2[C@H:33]1[C@@H:37]2[O:38][C:39]([CH3:41])([CH3:42])[O:40][C@H:36]2[C@H:35]([CH:43]=[O:44])[O:34]1

Participants

6

Reactant 3

HCID 24477Sodium ThiosulfateHCID 159087TriacetoxyperiodinaneHCID 117271506-Chloro-9-[2,3-O-(1-methylethylidene)-beta-D-ribofuranosyl]-9H-Purine

Product 1

HCID 86607307(3aR,4R,6R,6aR)-6-(6-Chloro-9H-purin-9-yl)-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxol-4-carbaldehydeYield 86%

Reagents, catalysts & solvents 2

HCID 159087TriacetoxyperiodinaneCatalystHCID 6344DichloromethaneSolvent2×

Procedure

To a suspension of Dess-Martin periodinane (16.42 g, 0.03872 mol) in anhydrous methylene chloride (88.0 mL) cooled in an ice/water bath was added [(3aR,4R,6R,6aR)-6-(6-chloro-9H-purin-9-yl)-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxol-4-yl]methanol (11.50 g, 0.03520 mol) in methylene chloride (200 mL). The reaction was stirred under an atmosphere of nitrogen and allowed to warm to ambient temperature. After 2 hours, a further portion of Dess-Martin periodinane (1.00 g, 0.00236 mol) was added. After 3 hours, a solution (200 mL) of sodium thiosulfate (50 g in 200 mL of saturated aqueous sodium bicarbonate) was added and the mixture stirred for 10 min. The aqueous was extracted 2×250 mL methylene chloride and 8×50 mL of chloroform. The combined organics were washed with water and dried over magnesium sulfate and concentrated in vacuo to dryness. The residue was taken up in dry toluene (200 mL) and concentrated in vacuo, and then taken up in dry methylene chloride and concentrated in vacuo to yield the product as a foam (9.83 g, 86%).

Workup

  1. temperaturecooled in an ice/water bath
  2. waitAfter 3 hours
  3. stirringthe mixture stirred for 10 min
  4. extractionThe aqueous was extracted 2×250 mL methylene chloride and 8×50 mL of chloroform
  5. washThe combined organics were washed with water
  6. dry with materialdried over magnesium sulfate
  7. concentrationconcentrated in vacuo to dryness
  8. concentrationconcentrated in vacuo
  9. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-6df79687c84b4e14884c1c17a5ca154e
Source dataset
uspto-grants-2011_05
Patent number
US07951810B2

Reaction notes

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