p-Fluoronitrobenzene → HCID 58256418, compound

HRID 1805240Notes

Reaction equation

HRID 1805240 reaction equation
[C:1]([O:5][C:6]([N:8]1[C@@H:12]([CH2:13][C@@H:14]([OH:19])[C:15]([F:18])([F:17])[F:16])[CH2:11][O:10][C:9]1([CH3:21])[CH3:20])=[O:7])([CH3:4])([CH3:3])[CH3:2].F[C:23]1[CH:28]=[CH:27][C:26]([N+:29]([O-:31])=[O:30])=[CH:25][CH:24]=1.C[Si]([N-][Si](C)(C)C)(C)C.[K+]>C1COCC1.ClCCl>[C:1]([O:5][C:6]([N:8]1[C@@H:12]([CH2:13][C@@H:14]([O:19][C:23]2[CH:28]=[CH:27][C:26]([N+:29]([O-:31])=[O:30])=[CH:25][CH:24]=2)[C:15]([F:18])([F:16])[F:17])[CH2:11][O:10][C:9]1([CH3:21])[CH3:20])=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

6

Reactant 3

HCID 9590p-FluoronitrobenzeneHCID 3251421Potassium bis(trimethylsilyl)amideHCID 58256397HCID 58256397, compound

Product 1

HCID 58256418HCID 58256418, compoundYield 97%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To a cooled, stirred solution of (S)-2,2-dimethyl-4-((R)-3,3,3-trifluoro-2-hydroxy-propyl)-oxazolidine-3-carboxylic acid tert-butyl ester (1.99 g) and 1-fluoro-4-nitrobenzene (0.69 ml) in THF (20 ml) at 0° C. was added dropwise potassium bis(trimethylsilyl)amide solution (7.7 ml, 1 M solution in THF). The reaction mixture was stirred for 30 min at 0° C., then allowed to warm to room temperature and stirred for a further 1 h. The mixture was then diluted with dichloromethane and washed with sat. aq. ammonium chloride solution. The phases were separated and the aqueous phase was extracted with dichloromethane. The combined organic phases were dried over sodium sulfate and concentrated in vacuo. The residue was purified by column chromatography (SiO2; gradient: heptane/EtOAc) to give (S)-2,2-dimethyl-4-[(R)-3,3,3-trifluoro-2-(4-nitro-phenoxy)-propyl]-oxazolidine-3-carboxylic acid tert-butyl ester as a yellow viscous oil (2.7 g, 97%). MS (ISP): 435.3 ([M+H]+), 379.3 ([M+H—C4H8]+), 335.4 ([M+H—C4H8—CO2]+).

Workup

  1. temperatureto warm to room temperature
  2. stirringstirred for a further 1 h
  3. washwashed with sat. aq. ammonium chloride solution
  4. customThe phases were separated
  5. extractionthe aqueous phase was extracted with dichloromethane
  6. dry with materialThe combined organic phases were dried over sodium sulfate
  7. concentrationconcentrated in vacuo
  8. customThe residue was purified by column chromatography (SiO2; gradient: heptane/EtOAc)

Sources & evidence

ORD record
ord-f9beb45edb274796adf606cc591d6f23
Source dataset
uspto-grants-2013_01
Patent number
US08354441B2

Reaction notes

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