Water → HCID 58348421, compound

HRID 2192321Notes

Reaction equation

HRID 2192321 reaction equation
[CH3:1][O:2][C:3](=[O:12])[CH2:4][C:5]1[CH:10]=[CH:9][CH:8]=[C:7]([F:11])[CH:6]=1.C[Si]([N-][Si](C)(C)C)(C)C.[Li+].Br[CH2:24][CH2:25][CH:26]=[CH2:27].O>O1CCCC1>[CH3:1][O:2][C:3](=[O:12])[C:4]([CH2:6][CH2:5][CH:4]=[CH2:3])([C:5]1[CH:10]=[CH:9][CH:8]=[C:7]([F:11])[CH:6]=1)[CH2:24][CH2:25][CH:26]=[CH2:27]

Participants

6

Reactant 4

HCID 962WaterHCID 21241Homoallyl bromide3×HCID 2733832Lithium Hexamethyldisilazide3×HCID 2734108Methyl 3-fluorophenylacetate

Product 1

HCID 58348421HCID 58348421, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

(3-Fluoro-phenyl)-acetic acid methyl ester (4.30 g) was dissolved in tetrahydrofuran (20 mL) and cooled to −78° C. Lithium bis(trimethylsilyl)amide (25.6 mL, 1M THF solution) was added and the solution was stirred for 30 minutes. 4-Bromo-but-1-ene (2.60 mL) was added and the reaction contents were allowed to warm to room temperature and stir for an hour. The reaction mixture was again cooled to −78° C. Lithium bis(trimethylsilyl)amide (25.6 mL, 1M THF solution) was added and the solution was stirred for 30 minutes. 4-Bromo-1-butene (2.60 mL) was added and the reaction mixture was allowed to warm to room temperature and stir for an hour. The contents were again cooled to −78° C. and further aliquots of Lithium bis(trimethylsilyl)amide (25.6 mL, 1M THF solution) and 4-bromo-1-butene (2.60 mL) were added following the procedure outlined above. After stirring overnight, water (20 mL) was added and the reaction mixture extracted with diethyl ether (2×60 mL). The combined organic extracts were dried with magnesium sulfate and evaporated. The resulting liquid was purified by column chromatography on silica eluting with ethyl acetate/isohexane (1/99) to afford the sub-titled compound (5.0 g).

Workup

  1. customthe reaction contents
  2. temperatureto warm to room temperature
  3. stirringstir for an hour
  4. temperatureThe reaction mixture was again cooled to −78° C
  5. stirringthe solution was stirred for 30 minutes
  6. temperatureto warm to room temperature
  7. stirringstir for an hour
  8. temperatureThe contents were again cooled to −78° C.
  9. stirringAfter stirring overnight
  10. extractionthe reaction mixture extracted with diethyl ether (2×60 mL)
  11. dry with materialThe combined organic extracts were dried with magnesium sulfate
  12. customevaporated
  13. customThe resulting liquid was purified by column chromatography on silica eluting with ethyl acetate/isohexane (1/99)

Sources & evidence

ORD record
ord-e3925ed6455c4bb7ab20e36b407e2be2
Source dataset
uspto-grants-2012_12
Patent number
US08329729B2

Reaction notes

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