Dimethyl Sulfoxide → 3,4-Di-O-i-propyl-6-deoxy-L-glucal

HRID 611802Notes

Reaction equation

HRID 611802 reaction equation
[CH:1](I)([CH3:3])[CH3:2].C([O:8][C@@H:9]1[C@@H:14]([O:15][C:16](=O)[CH3:17])[C@H:13]([CH3:19])[O:12][CH:11]=[CH:10]1)(=O)C.[OH-].[Na+].[CH3:22]S(C)=O>S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC>[CH:1]([O:8][C@@H:9]1[C@@H:14]([O:15][CH:16]([CH3:17])[CH3:22])[C@H:13]([CH3:19])[O:12][CH:11]=[CH:10]1)([CH3:3])[CH3:2]

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 6362Isopropyl iodideHCID 14798Sodium HydroxideHCID 2734733L-arabino-Hex-1-enitol, 1,5-anhydro-2,6-dideoxy-, diacetate

Product 1

HCID 183962693,4-Di-O-i-propyl-6-deoxy-L-glucalYield 28%

Reagents, catalysts & solvents 1

HCID 94433Tetrabutylammonium hydrogen sulfateCatalyst

Procedure

i-Propyl iodide (40 mL, 0.40 mol), 3,4-di-O-acetyl-6-deoxy-L-glucal (4.28 g, 0.20 mol), 50% aqueous NaOH (43 mL, 0.81 mol) and DMSO (11.4 mL, 0.16 mol) were added sequentially to a 300 mL round-bottom, three-neck flask equipped with an overhead stirrer. Stirring was begun and tetrabutylammonium hydrogen sulfate (2.04 g, 0.006 mol) added in a single portion. The mixture was stirred for 67 h. at room temperature and for 24 h at reflux temperature. The mixture was cooled to room temperature and partitioned between water and pentane. The aqueous layer was extracted with additional pentane. The combined organic layers were successively washed with water (four times), dilute aqueous sodium thiosulfate, water, and saturated sodium bicarbonate. The solvent was removed under reduced pressure (20 Torr followed by 0.1 Torr) to yield a light yellow oil (1.2 g, 28%) that could be used without further purification. 1H NMR d 6.29 (dd, J=6.1, 1.4, 1 H), 4.70 (dd, J=6.1, 2.4, 1 H), 1.35 (d, J=6.4, 3 H), 1.21 (d, J=6.4, 3 H), 1.18 (d, J=6.4, 6 H), 1.17 (d, J=6.4, 3 H).

Workup

  1. customthree-neck flask equipped with an overhead stirrer
  2. stirringThe mixture was stirred for 67 h. at room temperature and for 24 h
  3. temperatureat reflux temperature
  4. custompartitioned between water and pentane
  5. extractionThe aqueous layer was extracted with additional pentane
  6. washThe combined organic layers were successively washed with water (four times), dilute aqueous sodium thiosulfate, water, and saturated sodium bicarbonate
  7. customThe solvent was removed under reduced pressure (20 Torr followed by 0.1 Torr)

Sources & evidence

ORD record
ord-2c38c4e6b32a4003aad83312f5a79e2b
Source dataset
uspto-grants-1999_12
Patent number
US06001981

Reaction notes

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