Hydrochloric Acid → (R)-4-Benzyl-3-[5-(tert-butyl-diphenyl-silanyloxy)-pentanoyl]-oxazolidin-2-one

HRID 1169226Notes

Reaction equation

HRID 1169226 reaction equation
[C:1](Cl)(=O)[C:2]([CH3:5])(C)[CH3:3].C(N(CC)CC)C.[C:15]([Si:19]([C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)([C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1)[O:20][CH2:21][CH2:22][CH2:23][CH2:24][C:25]([OH:27])=O)([CH3:18])([CH3:17])[CH3:16].[O:40]1[CH2:44][CH2:43][NH:42][C:41]1=[O:45].[CH2:46]([Li])[CH2:47][CH2:48]C.Cl>CCOCC.C1COCC1.CCCCCC>[CH2:3]([C@@H:43]1[CH2:44][O:40][C:41](=[O:45])[N:42]1[C:25](=[O:27])[CH2:24][CH2:23][CH2:22][CH2:21][O:20][Si:19]([C:15]([CH3:18])([CH3:17])[CH3:16])([C:28]1[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=1)[C:34]1[CH:35]=[CH:36][CH:37]=[CH:38][CH:39]=1)[C:2]1[CH:5]=[CH:48][CH:47]=[CH:46][CH:1]=1

Participants

10

Reactant 6

HCID 313Hydrochloric AcidHCID 8471TriethylamineHCID 62493Pivaloyl chlorideHCID 739492-OxazolidinoneHCID 14333793Pentanoic acid, 5-[[(1,1-dimethylethyl)diphenylsilyl]oxy]-HCID 178418339Butyllithium

Product 1

HCID 59094988(R)-4-Benzyl-3-[5-(tert-butyl-diphenyl-silanyloxy)-pentanoyl]-oxazolidin-2-oneYield 80.7%

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Procedure

To a stirring solution of pivaloyl chloride (3.39 mL, 27.5 mmol) and triethylamine (4.39 mL, 31.4 mmol) in dry ether in a flame-dried round bottom flask under N2 at 0° C. was added 5-(tert-butyl-diphenyl-silanyloxy)-pentanoic acid prepared according to procedures of Barrett, A. G. M. ; et al J. Org. Chem. (1989), 54(14), 3321 (9.35 g, 26.2 mmol). The reaction was warmed to room temperature, and, after 25 min, the white precipitate was removed by filtration. The filtrate was concentrated in vacuo to a colorless oil. The oil was dissolved in dry ether (6 mL) and added via cannula to a solution of lithiated oxazolidinone prepared by treating a solution of oxazolidinone (4.64 g, 26.2 mmol) in dry THF (150 mL) in a flame-dried round bottom flask under N2 at −78° C. with n-butyllithium in hexane (22.4 mL, 1.17 M) until the solution became pale yellow in color. The reaction was stirred for 40 min and then poured into 1N aqueous hydrogen chloride. The reaction was extracted with ethyl acetate (3×150 mL). The organic layers were combined, washed with saturated aqueous sodium bicarbonate, brine, dried over sodium sulfate, and concentrated in vacuo to a colorless oil. The oil was purified by flash chromatography (SiO2, 5-30% ethyl acetate in hexanes) to yield 10.9 g (80.7%) of a white solid. MS (APCI), m+/z: (M+H)+=516.5.

Workup

  1. customprepared
  2. customthe white precipitate was removed by filtration
  3. concentrationThe filtrate was concentrated in vacuo to a colorless oil
  4. dissolutionThe oil was dissolved in dry ether (6 mL)
  5. additionadded via cannula to a solution of lithiated oxazolidinone
  6. customprepared
  7. extractionThe reaction was extracted with ethyl acetate (3×150 mL)
  8. washwashed with saturated aqueous sodium bicarbonate, brine
  9. dry with materialdried over sodium sulfate
  10. concentrationconcentrated in vacuo to a colorless oil
  11. customThe oil was purified by flash chromatography (SiO2, 5-30% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-ee6c66a0e25c4a04958de4f2a5e0d918
Source dataset
uspto-grants-2003_09
Patent number
US06627629B2

Reaction notes

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