Chlorotrimethylsilane → HCID 86584023, compound

HRID 1280744Notes

Reaction equation

HRID 1280744 reaction equation
[Li]CCCC.C(NC(C)C)(C)C.[C:13]1([CH2:19][CH2:20][CH2:21][C:22]([O:24][CH3:25])=[O:23])[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.C[Si](C)(C)Cl.C1C=CC(S(N(S(C2C=CC=CC=2)(=O)=O)[F:41])(=O)=O)=CC=1>C1COCC1.C(Cl)Cl>[CH3:25][O:24][C:22](=[O:23])[CH:21]([F:41])[CH2:20][CH2:19][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

8

Reactant 5

HCID 6397ChlorotrimethylsilaneHCID 7912DiisopropylamineHCID 281254Methyl 4-phenylbutyrateHCID 588007N-FluorobenzenesulfonimideHCID 178418339Butyllithium

Product 1

HCID 86584023HCID 86584023, compoundYield 63%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

nBuLi (13.8 ml, 22 mmol, 1.6 M in hexane) was added dropwise into a 0° C. solution of diisopropylamine (3.39 ml,24 mmol) in THF (34 ml). The reaction mixture was stirred at 0° C. for 15 minutes then cooled to −75 ° C. and treated slowly with a solution of methyl 4-phenylbutyrate (3.56 g, 20 mmol) in THF (10 ml). After 30 minutes stirring at −75° C., trimethylchlorosilane ( 5.06 ml, 40 mmol) was added dropwise and the reaction mixture was allowed to warm up to room temperature. After 30 minutes, reaction mixture was concentrated, the residue was taken up in CH2Cl2 (100 ml), the resulting precipitate was filtered, filtrate was cooled to 13° C. and subsequently treated slowly with a solution of N-fluorodibenzenesulfonimide (6.3 g, 20 mmol) in CH2Cl2 (50 ml). After 3 hours stirring at room temperature, the reaction mixture was washed with H2O (2 times). The aqueous phase was extracted with CH2Cl2, the combined organic phases were dried over Na2SO4 and concentrated. The residue was chromatographed over silica gel (hexane-ethylacetate 99:1 then 98:2) to provide (RS)-2-fluoro-4-phenyl-butyric acid methyl ester (2.47 g, 63%) as a colorless oil, MS: m/e=196.1 (M+).

Workup

  1. temperaturethen cooled to −75 ° C.
  2. stirringAfter 30 minutes stirring at −75° C.
  3. temperatureto warm up to room temperature
  4. waitAfter 30 minutes
  5. customreaction mixture
  6. concentrationwas concentrated
  7. filtrationthe resulting precipitate was filtered
  8. temperaturefiltrate was cooled to 13° C.
  9. stirringAfter 3 hours stirring at room temperature
  10. washthe reaction mixture was washed with H2O (2 times)
  11. extractionThe aqueous phase was extracted with CH2Cl2
  12. dry with materialthe combined organic phases were dried over Na2SO4
  13. concentrationconcentrated
  14. customThe residue was chromatographed over silica gel (hexane-ethylacetate 99:1

Sources & evidence

ORD record
ord-895ad4de431c4de6b91cb874b6714a46
Source dataset
uspto-grants-2002_09
Patent number
US06451819B2

Reaction notes

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