(2R,3R)-4-(2',5'-dimethoxy-3',4',6'-trimethylphenyl)-2,3-epoxy-2-methylbutanol → (S)-4-(2,5-dimethoxy-3,4,6-trimethylphenyl)-2-methyl-1,2-butanediol

HRID 1789600Notes

Reaction equation

HRID 1789600 reaction equation
[CH3:1][O:2][C:3]1[C:8]([CH3:9])=[C:7]([CH3:10])[C:6]([O:11][CH3:12])=[C:5]([CH3:13])[C:4]=1[CH2:14][C@H:15]1[O:20][C@:16]1([CH3:19])[CH2:17][OH:18].[H][H]>CO.O.[Ni]>[CH3:1][O:2][C:3]1[C:8]([CH3:9])=[C:7]([CH3:10])[C:6]([O:11][CH3:12])=[C:5]([CH3:13])[C:4]=1[CH2:14][CH2:15][C@:16]([CH3:19])([OH:20])[CH2:17][OH:18]

Participants

6

Reactant 2

HCID 18602181(2R,3R)-4-(2',5'-dimethoxy-3',4',6'-trimethylphenyl)-2,3-epoxy-2-methylbutanolHCID 178418361HCID 178418361, compound

Product 1

HCID 11129761(S)-4-(2,5-dimethoxy-3,4,6-trimethylphenyl)-2-methyl-1,2-butanediolYield 86.4%

Reagents, catalysts & solvents 3

HCID 935NickelCatalystHCID 887MethanolSolventHCID 962WaterSolvent

Procedure

185 mg of (2R,3R)-4-(2',5'-dimethoxy-3',4',6'-trimethylphenyl)-2,3-epoxy-2-methylbutanol are dissolved in 5 ml of methanol and the solution is subsequently diluted with 5 ml of water. Thereupon, Raney-nickel is added and the mixture is heated at reflux under hydrogen for 2 hours. After the hydrogen uptake has finished the mixture is filtered, the filter residue is washed with methanol and methylene chloride and the combined filtrate and washings are concentrated on a rotary evaporator. Residual water is distilled off azeotropically by the addition of methylene chloride. The oil obtained is recrystallized from n-hexane/diethyl ether and there are obtained 161 mg of 55% (S)-4-(2',5'-dimethoxy-3',4',6'-trimethylphenyl)-2-methyl-1,2-butanediol (48% yield; GC analysis of the acetonide). Data of the pure substance: M.p. 86°-87° C.; [α]D20 +2.55° (c=5.3% in CHCl3).

Workup

  1. temperaturethe mixture is heated
  2. temperatureat reflux under hydrogen for 2 hours
  3. filtrationis filtered
  4. washthe filter residue is washed with methanol and methylene chloride
  5. concentrationthe combined filtrate and washings are concentrated on a rotary evaporator
  6. distillationResidual water is distilled off azeotropically by the addition of methylene chloride
  7. customThe oil obtained
  8. customis recrystallized from n-hexane/diethyl ether and there

Sources & evidence

ORD record
ord-a0d5e8a417344026b54840fa34c293db
Source dataset
uspto-grants-1987_08
Patent number
US04689427

Reaction notes

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