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

HRID 705237Notes

Reaction equation

HRID 705237 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-178f7d5e5f4e47ffb61855a6ee11c7d7
Source dataset
uspto-grants-2015_11
Patent number
US09173883B2

Reaction notes

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