Allyl bromide → HCID 67490889, compound

HRID 1917378Notes

Reaction equation

HRID 1917378 reaction equation
[CH2:1](Br)[CH:2]=[CH2:3].[C:5]([O:9][C:10]([C@@:12]1([CH2:26][CH:27]=[CH2:28])[CH2:16][C:15](=[O:17])[N:14]([C@@H:18]([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[CH3:19])[CH2:13]1)=[O:11])([CH3:8])([CH3:7])[CH3:6].C[Si](C)(C)[N-][Si](C)(C)C.[Li+].[Cl-].[NH4+]>O1CCCC1.O>[C:5]([O:9][C:10]([C@@:12]1([CH2:26][CH:27]=[CH2:28])[C@@H:16]([CH2:3][CH:2]=[CH2:1])[C:15](=[O:17])[N:14]([C@@H:18]([C:20]2[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=2)[CH3:19])[CH2:13]1)=[O:11])([CH3:8])([CH3:7])[CH3:6]

Participants

7

Reactant 4

HCID 7841Allyl bromideHCID 25517Ammonium ChlorideHCID 2733832Lithium HexamethyldisilazideHCID 67490875(3S)-3-Allyl-5-oxo-1-[(1R)-1-phenylethyl]pyrrolidine-3-carboxylic acid tert-butyl ester

Product 1

HCID 67490889HCID 67490889, compoundYield 44.4%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

Allyl bromide (1.36 mL, 16.1 mmol) was added to a solution of (3S)-3-allyl-5-oxo-1-[(1R)-1-phenylethyl]pyrrolidine-3-carboxylic acid tert-butyl ester (4.05 g, 12.3 mmol) in tetrahydrofuran (41.0 mL) with stirring under salt ice cooling. A 1 M solution of lithium hexamethyldisilazide in tetrahydrofuran (16.0 mL, 16.0 mmol) was added dropwise with stirring under salt ice cooling, and the mixture was stirred under salt ice cooling for 15 minutes. A saturated ammonium chloride solution (40 mL) and water (20 mL) were added to the reaction solution, followed by extraction with ethyl acetate (40 mL×1, 20 mL×1). The organic layer was washed with brine (140 mL) and dried over anhydrous sodium sulfate. After filtration, the filtrate was concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate=100:0→90:10→89:11→88:12→87:13→83:17→80:20→75:25) to give 2.02 g of the title compound.

Workup

  1. stirringwith stirring under salt ice cooling
  2. stirringthe mixture was stirred under salt ice cooling for 15 minutes
  3. extractionfollowed by extraction with ethyl acetate (40 mL×1, 20 mL×1)
  4. washThe organic layer was washed with brine (140 mL)
  5. dry with materialdried over anhydrous sodium sulfate
  6. filtrationAfter filtration
  7. concentrationthe filtrate was concentrated under reduced pressure
  8. customThe resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate=100:0→90:10→89:11→88:12→87:13→83:17→80:20→75:25)

Sources & evidence

ORD record
ord-dced857191ec4b899e399adbd6c69c08
Source dataset
uspto-grants-2013_12
Patent number
US08618094B2

Reaction notes

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