Carbon Dioxide → HCID 70168489, compound

HRID 992799Notes

Reaction equation

HRID 992799 reaction equation
[C:1]([O:11][CH3:12])(=[O:10])[C@H:2]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)[OH:3].[C:13](=O)([O-:15])[O-:14].[Cs+].[Cs+].C(=O)=O.COC1C=CC(CCl)=CC=1>CN(C)C=O>[CH2:2]([O:3][C:13](=[O:14])[OH:15])[C:4]1[CH:5]=[CH:6][CH:7]=[CH:8][CH:9]=1.[C:1]([O:11][CH3:12])(=[O:10])[CH:2]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)[OH:3]

Participants

6

Reactant 4

HCID 280Carbon DioxideHCID 10796Cesium carbonateHCID 699934-Methyloxybenzyl chlorideHCID 643570methyl (2S)-2-hydroxy-2-phenylacetate

Product 1

HCID 70168489HCID 70168489, compoundYield 190.7%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Methyl (S)-(+)-mandelate (332 mg, 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 4-methoxybenzyl chloride (0.81 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 607 mg of the desired methyl mandelate benzyl carbonate (92%): IR (thin film) 3036, 2957, 2838, 1748, 1614, 1517, 1456, 1383, 1246, 1175, 1028, 928, 824 cm−1; 1H NMR (360 MHz, CDCl3) d 3.73 (s, 3H), 3.79 (s, 3H), 5.16 (s, 2 H), 5.88 (s, 1H), 6.88-7.48 (m, 9 H); 13C NMR (90 MHz, CDCl3) d 52.57, 55.11, 70.04, 113.81, 127.47, 128.67, 129.30, 130.26, 133.10, 154.27, 159.83, 168.90. EM Anal. Calcd. C18H18O6: C, 65.45; H, 5.49. Found: C, 65.51; H, 5.55.

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-6d04b68f40d344a195ae18056052a3ae
Source dataset
uspto-grants-2002_10
Patent number
US06469193B1

Reaction notes

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