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Chlorotrimethylsilane → (E)-4-cyclopentyl-2-(3,4-difluoro-phenyl)-but-2-enoic acid methyl ester

HRID 276228
Notes
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Reaction equation

HRID 276228 reaction equation
BrCCBr.C[Si](Cl)(C)C.[CH3:10][O:11][C:12](=[O:22])/[C:13](/I)=[CH:14]\[CH2:15][CH:16]1[CH2:20][CH2:19][CH2:18][CH2:17]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[F:42][C:43]1[CH:44]=[C:45](I)[CH:46]=[CH:47][C:48]=1[F:49].[Cl-].[NH4+]>O1CCCC1.[Zn].C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd]>[CH3:10][O:11][C:12](=[O:22])/[C:13](/[C:46]1[CH:45]=[CH:44][C:43]([F:42])=[C:48]([F:49])[CH:47]=1)=[CH:14]/[CH2:15][CH:16]1[CH2:20][CH2:19][CH2:18][CH2:17]1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

10

Reactant 6

HCID 6397ChlorotrimethylsilaneHCID 78391,2-DibromoethaneHCID 11776TriphenylphosphineHCID 25517Ammonium ChlorideHCID 27244441,2-Difluoro-4-iodobenzeneHCID 86584748(E)-4-cyclopentyl-2-iodo-but-2-enoic acid methyl ester

Product 1

HCID 67483006
(E)-4-cyclopentyl-2-(3,4-difluoro-phenyl)-but-2-enoic acid methyl ester
Yield 73.1%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalyst6×HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 8028TetrahydrofuranSolvent5×

Conditions

Temperature
25 °C

Procedure

A mixture of zinc dust (0.98 g, 15 mmol, Aldrich, −325 mesh) and dry tetrahydrofuran (3 mL) under argon was treated with 1,2-dibromoethane (0.14 g, 0.75 mmol). The zinc suspension was then heated with a heat gun to ebullition, allowed to cool, and heated again. This process was repeated three times to make sure the zinc dust was activated. The activated zinc dust suspension was then treated with trimethylsilyl chloride (82 mg, 0.75 mmol), and the suspension was stirred for 15 min at 25° C. The reaction mixture was then treated dropwise with a solution of (E)-4-cyclopentyl-2-iodo-but-2-enoic acid methyl ester (prepared in Example 21, 1.47 g, 5 mmol) in dry tetrahydrofuran (1.5 mL) over 3 min. After the addition, the reaction mixture was stirred for 1 h at 40-45° C. and then stirred overnight at 25° C. The reaction mixture was then diluted with dry tetrahydrofuran (5 mL), and the stirring was stopped to allow the excess zinc dust to settle down (˜2 h). In a separate reaction flask, bis(dibenzylideneacetone)palladium(0) (54 mg, 0.1 mmol) and triphenylphosphine (104 mg, 0.4 mmol) in dry tetrahydrofuran (10 mL) was stirred at 25° C. under argon for 10 min and then treated with 3,4-difluoro-iodobenzene (0.96 g, 4 mmol) and the freshly prepared zinc compound in tetrahydrofuran. The resulting brick red solution was heated at 25° C. for 15 h, at which time, thin layer chromatography analysis of the reaction mixture indicated the absence of starting material. The reaction mixture was cooled to 25° C. and then poured into a saturated aqueous ammonium chloride solution (50 mL), and the organic compound was extracted into diethyl ether (2×50 mL). The combined ether extracts were washed with a saturated aqueous sodium chloride solution (1×50 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo. Biotage chromatography (FLASH 40M, Silica, 4/1 hexanes/diethyl ether) afforded (E)-4-cyclopentyl-2-(3,4-difluoro-phenyl)-but-2-enoic acid methyl ester (0.82 g, 73%) as a viscous oil: EI-HRMS m/e calcd for C16H18F2O2 (M+) 280.1275, found 280.1275.

Workup

  1. temperatureto cool
  2. temperatureheated again
  3. additionAfter the addition
  4. stirringthe reaction mixture was stirred for 1 h at 40-45° C.
  5. stirringstirred overnight at 25° C
  6. custom(˜2 h)
  7. stirringwas stirred at 25° C. under argon for 10 min
  8. temperatureThe resulting brick red solution was heated at 25° C. for 15 h, at which time, thin layer chromatography analysis of the reaction mixture
  9. temperatureThe reaction mixture was cooled to 25° C.
  10. extractionthe organic compound was extracted into diethyl ether (2×50 mL)
  11. washThe combined ether extracts were washed with a saturated aqueous sodium chloride solution (1×50 mL)
  12. dry with materialdried over anhydrous magnesium sulfate
  13. filtrationfiltered
  14. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-e276cf048c4a4a17a90ac9badd758739
Source dataset
uspto-grants-2002_03
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US06353111B1

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes