Tetrahydrofuran → (S)-5-(2-Hydroxyethyl)-2,2-dimethyl-1,3-dioxolan-4-one

HRID 2257234Notes

Reaction equation

HRID 2257234 reaction equation
O1CCOC1C([O-])=O.[C:9]([OH:17])(=[O:16])[C@H:10]([CH2:12][C:13]([OH:15])=O)[OH:11].O1C[CH2:21][CH2:20][CH2:19]1>COC(OC)(C)C.C1(C)C=CC(S(O)(=O)=O)=CC=1>[OH:15][CH2:13][CH2:12][C@@H:10]1[O:11][C:20]([CH3:21])([CH3:19])[O:17][C:9]1=[O:16]

Participants

6

Reactant 3

HCID 8028TetrahydrofuranHCID 222656L-Malic Acid2×HCID 21503118Dioxolanate

Product 1

HCID 10975778(S)-5-(2-Hydroxyethyl)-2,2-dimethyl-1,3-dioxolan-4-one

Reagents, catalysts & solvents 2

HCID 6101p-Toluenesulfonic acidCatalystHCID 64952,2-DimethoxypropaneCatalyst

Procedure

In a 500 mL flame-dried round bottom flask fitted with a septum and under argon was placed 11.0 g (63.2 mmol) of the dioxolanate of (S)-malic acid (prepared by reaction of commercially available (S)-malic acid with excess dimethoxypropane and p-toluenesulfonic acid as a catalyst) dissolved in 200 mL anhydrous tetrahydrofuran. The reaction was cooled (-20° C. to -30° C.) and 70 mL of 1M borane-tetrahydrofuran complex was added dropwise over 2 hours. Following addition the reaction vessel was placed in a refrigerator at 4° C. for 11 hours, warmed to room temperature, stirred at room temperature for 9 hours and chromatographed (silica gel) using acetone as eluant. Following evaporation under reduced pressure, the residue was chromatographed as before to generate 9.1 g (90%) of the alcohol as a colorless unstable liquid which was dried under reduced pressure and utilized as such in the next reaction: IR (neat, cm-1) 3480 (br), 2994, 2940, 2888, 1791, 1220; 1H NMR (CDCl3) δ 4.58 (dd, J=5.1, 7.0 Hz, 1H), 3.91-3.79 (m, 2H), 2.28-2.13 (m, 1H), 2.13-1.97 (m, 1H), 1.64 (s, 3H), 1.57 (s, 3H).

Workup

  1. customIn a 500 mL flame-dried round bottom flask
  2. customfitted with a septum and under argon
  3. temperatureThe reaction was cooled (-20° C. to -30° C.) and 70 mL of 1M borane-tetrahydrofuran complex
  4. additionwas added dropwise over 2 hours
  5. additionaddition the reaction vessel
  6. customchromatographed (silica gel)
  7. customevaporation under reduced pressure
  8. customthe residue was chromatographed as before
  9. customwas dried under reduced pressure
  10. customsuch in the next reaction

Sources & evidence

ORD record
ord-a06646acd8a748b494367f4fd2274067
Source dataset
uspto-grants-1997_08
Patent number
US05656662

Reaction notes

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