Hydrogen Peroxide → tert-butyl (2RS,3RS)-2-(3,4-dichlorobenzyl)-3-hydroxybutanoate

HRID 52859Notes

Reaction equation

HRID 52859 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:17]=[CH:18][C:19]=1[Cl:20])[CH2:5][CH:6]([C:14]([CH3:16])=[O:15])[C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8].C([BH-](C(CC)C)C(CC)C)(CC)C.[Li+].[OH-].[Na+].OO>O1CCCC1.CCCCCC.O>[Cl:1][C:2]1[CH:3]=[C:4]([CH:17]=[CH:18][C:19]=1[Cl:20])[CH2:5][CH:6]([CH:14]([OH:15])[CH3:16])[C:7]([O:9][C:10]([CH3:13])([CH3:11])[CH3:12])=[O:8]

Participants

8

Reactant 4

HCID 784Hydrogen PeroxideHCID 14798Sodium HydroxideHCID 3611392Lithium tri-s-butylborohydrideHCID 19073669Tert-butyl 2-(3,4-dichlorobenzyl)acetoacetate

Product 1

HCID 53695590tert-butyl (2RS,3RS)-2-(3,4-dichlorobenzyl)-3-hydroxybutanoateYield 35.9%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
-70 °C

Procedure

10.5 g of tert-butyl 2-(3,4-dichlorobenzyl)acetoacetate (which was prepared by treating 3,4-dichlorobenzyl chloride and tert-butyl acetoacetate with potassium tert-butoxide in tert-butanol) was dissolved in 100 ml of tetrahydrofuran, and 45 ml of a 1M tetrahydrofuran solution of lithium tri-sec-butylborohydride was added thereto with stirring under cooling to -70° C. The mixture was stirred at the same temperature for 1 hour. Then, 20 ml of water and 15 ml of a 3N sodium hydroxide aqueous solution were added to the reaction solution, and 15 ml of a 30% hydrogen peroxide aqueous solution was dropwise added thereto with stirring under cooling to -20° C. The mixture was stirred at room temperature for 1 hour. Then, hexane was added to the reaction solution, and the organic layer was collected by separation, then washed with a saturated sodium chloride aqueous solution and dried over anhydrous magnesium sulfate. The drying agent was separated by filtration, and then the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography (hexane/ethyl acetate=10/1→5/1) to obtain 3.79 g (yield: 33%) of tert-butyl (2RS, 3RS)-2-(3,4-dichlorobenzyl)-3-hydroxybutanoate.

Workup

  1. stirringThe mixture was stirred at the same temperature for 1 hour
  2. additionwas dropwise added
  3. stirringwith stirring
  4. temperatureunder cooling to -20° C
  5. stirringThe mixture was stirred at room temperature for 1 hour
  6. customthe organic layer was collected by separation
  7. washwashed with a saturated sodium chloride aqueous solution
  8. dry with materialdried over anhydrous magnesium sulfate
  9. customThe drying agent was separated by filtration
  10. distillationthe solvent was distilled off under reduced pressure

Sources & evidence

ORD record
ord-254f6086c3394b339279d48bb5399aae
Source dataset
uspto-grants-1997_04
Patent number
US05616803

Reaction notes

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