Ammonium Chloride → tert-butyl (3R)-3-[(4S)-2-oxo-4-propan-2-yl-1,3-oxazolidine-3-carbonyl]octanoate

HRID 263439Notes

Reaction equation

HRID 263439 reaction equation
[CH:1]([C@H:4]1[CH2:8][O:7][C:6](=[O:9])[N:5]1[C:10](=[O:17])[CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH3:16])([CH3:3])[CH3:2].C([N-]C(C)C)(C)C.[Li+].Br[CH2:27][C:28]([O:30][C:31]([CH3:34])([CH3:33])[CH3:32])=[O:29].[Cl-].[NH4+]>O1CCCC1>[CH:1]([C@H:4]1[CH2:8][O:7][C:6](=[O:9])[N:5]1[C:10](=[O:17])[C@@H:11]([CH2:27][C:28]([O:30][C:31]([CH3:34])([CH3:33])[CH3:32])=[O:29])[CH2:12][CH2:13][CH2:14][CH2:15][CH3:16])([CH3:3])[CH3:2]

Participants

6

Reactant 4

HCID 25517Ammonium ChlorideHCID 79177tert-Butyl bromoacetateHCID 2724682Lithium diisopropylamideHCID 108576323-Heptanoyl-4-(S)-isopropyl-oxazolidin-2-one

Product 1

HCID 11360239tert-butyl (3R)-3-[(4S)-2-oxo-4-propan-2-yl-1,3-oxazolidine-3-carbonyl]octanoateYield 91.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
-78 °C

Procedure

A solution of 4-(S)-isopropyl-3-(1-oxoheptyl)-2-oxazolidinone (519 mg) in tetrahydrofuran (15 ml) was cooled to -15° C., a 0.58M solution (39 ml) of lithium diisopropylamide in tetrahydrofuran was added thereto under an atmosphere of nitrogen, and the resulting mixture was stirred at -78° C for 10 minutes. A solution of tert-butyl bromoacetate (1.7 ml) in tetrahydrofuran (5 ml) was then added thereto and the temperature was allowed to rise gradually to -55° C. over a period of 5.5 hours with stirring. The reaction mixture was poured into a 5% aqueous solution of ammonium chloride and extracted with ethyl acetate. The organic extract was successively washed with water and a saturated aqueous solution of sodium chloride, and dried over sodium sulfate. After the solvent was distilled off under reduced pressure, the residue was purified by column chromatography through silica gel using a 10:1 mixture of hexane and ethyl acetate as an eluent, to give 697 mg (91.2%) of the desired compound. Recrystallization from aqueous methanol gave rise to crystals having a m.p. of 51°-53° C.

Workup

  1. waitto rise gradually to -55° C. over a period of 5.5 hours
  2. stirringwith stirring
  3. extractionextracted with ethyl acetate
  4. extractionThe organic extract
  5. washwas successively washed with water
  6. dry with materiala saturated aqueous solution of sodium chloride, and dried over sodium sulfate
  7. distillationAfter the solvent was distilled off under reduced pressure
  8. customthe residue was purified by column chromatography through silica gel using
  9. additiona 10:1 mixture of hexane and ethyl acetate as an eluent

Sources & evidence

ORD record
ord-4c4ed678c32449d4b591a632e0e1e2ac
Source dataset
uspto-grants-1997_07
Patent number
US05643908

Reaction notes

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