Carbon Dioxide → HCID 70167656, compound

HRID 992800Notes

Reaction equation

HRID 992800 reaction equation
[C:1]([O:10][CH3:11])(=[O:9])[C@H:2]([CH2:4][C:5]([O:7][CH3:8])=[O:6])[OH:3].[C:12](=[O:15])([O-:14])[O-:13].[Cs+].[Cs+].C(=O)=O.[CH2:21](Cl)[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1>CN(C)C=O>[CH2:21]([O:15][C:12](=[O:14])[OH:13])[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1.[C:1]([O:10][CH3:11])(=[O:9])[CH:2]([CH2:4][C:5]([O:7][CH3:8])=[O:6])[OH:3]

Participants

6

Reactant 4

HCID 280Carbon DioxideHCID 7503Benzyl ChlorideHCID 10796Cesium carbonateHCID 10285815(S)-(-)-Dimethyl malate

Product 1

HCID 70167656HCID 70167656, compoundYield 65%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Dimethyl (S)-(−) malate (0.27 mL, 2 mmol) is dissolved in anhydrous N,N-dimethylforamide (8 mL), and powdered cesium carbonate (1.95 g, 6 mmol, 3 eq) is added. The suspension is then stirred at room temperature while passing carbon dioxide gas for 1 hour before benzyl chloride (0.69 mL, 6 mmol, 3 eq) is added to the solution. Carbon dioxide gas is continuously bubbled through the solution for another 2˜3 hours until the starting material is consumed. The reaction is quenched with water (20 mL) and extracted with EtOAc (3×20 mL). The resulting organic layer is washed consecutively with water (3×20 mL), brine (20 mL), and dried over anhydrous sodium sulfate. Filtration and concentration in vacuo provides an oil, which is purified by column chromatography (9:1 Hexanes-EtOAc) to yield 384 mg of the desired dimethyl malate benzyl carbonate (65%): IR (thin film) 3034, 2957, 1746, 1439, 1383, 1216, 1042, 909, 756, 699 cm−1; 1H NMR (360 MHz, CDCl3) d 2.93 (d, 2H, J=6.26 Hz), 3.71 (s, 3H), 3.78 (s, 3H), 5.22 (s, 2H, J=6.08 Hz), 7.34-7.38 (m, 5H); 13C NMR (90 MHz, CDCl3) d 35.60, 51.97, 52.55, 70.00, 71.13, 128.17, 128.43, 153.94, 168.80, 169.10.

Workup

  1. customfor 1 hour
  2. additionis added to the solution
  3. customCarbon dioxide gas is continuously bubbled through the solution for another 2˜3 hours until the starting material
  4. customis consumed
  5. customThe reaction is quenched with water (20 mL)
  6. extractionextracted with EtOAc (3×20 mL)
  7. washThe resulting organic layer is washed consecutively with water (3×20 mL), brine (20 mL)
  8. dry with materialdried over anhydrous sodium sulfate
  9. filtrationFiltration and concentration in vacuo
  10. customprovides an oil, which
  11. customis purified by column chromatography (9:1 Hexanes-EtOAc)

Sources & evidence

ORD record
ord-2978ac24f3f347fb9df866d421680c57
Source dataset
uspto-grants-2002_10
Patent number
US06469193B1

Reaction notes

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