Ethanol → (R)-tert-butyl 4-((1R,2S)-1-(tert-butyldimethylsilyloxy)-3-hydroxy-2-methylpropyl)-2,2-dimethyloxazolidine-3-carboxylate

HRID 879149Notes

Reaction equation

HRID 879149 reaction equation
C([C@@H]1COC(=O)N1[C:14](=[O:40])[C@H:15]([CH3:39])[C@H:16]([C@H:25]1[CH2:29][O:28][C:27]([CH3:31])([CH3:30])[N:26]1[C:32]([O:34][C:35]([CH3:38])([CH3:37])[CH3:36])=[O:33])[O:17][Si:18]([C:21]([CH3:24])([CH3:23])[CH3:22])([CH3:20])[CH3:19])C1C=CC=CC=1.C(O)C.[Li+].[BH4-]>C1COCC1.C(OCC)C.[OH-].[Na+]>[Si:18]([O:17][C@@H:16]([C@H:25]1[CH2:29][O:28][C:27]([CH3:31])([CH3:30])[N:26]1[C:32]([O:34][C:35]([CH3:36])([CH3:38])[CH3:37])=[O:33])[C@@H:15]([CH3:39])[CH2:14][OH:40])([C:21]([CH3:22])([CH3:23])[CH3:24])([CH3:20])[CH3:19]

Participants

7

Reactant 3

HCID 702EthanolHCID 4148881Lithium borohydrideHCID 68547408(R)-tert-butyl 4-((1R,2R)-3-((R)-4-benzyl-2-oxooxazolidin-3-yl)-1-(tert-butyldimethylsilyloxy)-2-methyl-3-oxopropyl)-2,2-dimethyloxazolidine-3-carboxylate

Product 1

HCID 59226545(R)-tert-butyl 4-((1R,2S)-1-(tert-butyldimethylsilyloxy)-3-hydroxy-2-methylpropyl)-2,2-dimethyloxazolidine-3-carboxylateYield 71%

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolventHCID 14798Sodium HydroxideSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of (R)-tert-butyl 4-((1R,2R)-3-((R)-4-benzyl-2-oxooxazolidin-3-yl)-1-(tert-butyldimethylsilyloxy)-2-methyl-3-oxopropyl)-2,2-dimethyloxazolidine-3-carboxylate (1.0 equiv.) and ethanol (3.0 equiv.) in THF (0.09 M) was added LiBH4 (3.0 equiv.) at −30° C. The reaction mixture was allowed to warm up to 0° C. and stirred at that temperature for 3 hours. The solution was then diluted with diethyl ether and 1N NaOH was added. The resulting mixture was extracted with ethyl acetate, the organic layer was separated, washed with sat. NaCl, dried over magnesium sulfate, filtered, and concentrated. The residue was purified via silica gel column chromatography eluting with ethyl acetate and hexanes (1:4) to give (R)-tert-butyl 4-((1R,2S)-1-(tert-butyldimethylsilyloxy)-3-hydroxy-2-methylpropyl)-2,2-dimethyloxazolidine-3-carboxylate as the major product (5:2 ratio) in 71% yield. LC/MS=304.3 (M+H-Boc), Rt=0.95 min (Frac 65%-95% method).

Workup

  1. additionwas added
  2. extractionThe resulting mixture was extracted with ethyl acetate
  3. customthe organic layer was separated
  4. washwashed with sat. NaCl
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was purified via silica gel column chromatography
  9. washeluting with ethyl acetate and hexanes (1:4)

Sources & evidence

ORD record
ord-f592922979d44bfeb656ea54bcecbf17
Source dataset
uspto-grants-2015_03
Patent number
US08987457B2

Reaction notes

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