Ammonium Chloride → Tert-butyl[(1s,5r,6r)-6-(aminomethyl)bicyclo[3.2.0]hept-3-en-6-yl]acetate

HRID 551615Notes

Reaction equation

HRID 551615 reaction equation
[C:1]([O:5][C:6](=[O:19])[CH2:7][C@:8]1([CH2:15][N+:16]([O-])=O)[CH2:14][C@H:13]2[C@@H:9]1[CH:10]=[CH:11][CH2:12]2)([CH3:4])([CH3:3])[CH3:2].[Cl-].[NH4+]>C(O)C.O.C(=O)(O)[O-].[Na+].C(OCC)(=O)C.[Fe]>[C:1]([O:5][C:6](=[O:19])[CH2:7][C@:8]1([CH2:15][NH2:16])[CH2:14][C@H:13]2[C@@H:9]1[CH:10]=[CH:11][CH2:12]2)([CH3:2])([CH3:4])[CH3:3]

Participants

8

Reactant 2

HCID 25517Ammonium ChlorideHCID 91600480Tert-butyl[(1s,5r,6r)-6-(nitromethyl)bicyclo[3.2.0]hept-3-en-6-yl]acetate

Product 1

HCID 66803936Tert-butyl[(1s,5r,6r)-6-(aminomethyl)bicyclo[3.2.0]hept-3-en-6-yl]acetateYield 28.7%

Reagents, catalysts & solvents 5

HCID 23925IronCatalyst2×HCID 702EthanolSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolventHCID 516892Sodium BicarbonateSolvent

Procedure

Tert-butyl[(1S,5R,6R)-6-(nitromethyl)bicyclo[3.2.0]hept-3-en-6-yl]acetate (peak 1, 21.6 g, 80.8 mmol) was dissolved in ethanol (200 mL) and water (100 mL). To the solution, iron powder (45.1 g, 80.8 mmol) and ammonium chloride (2.59 g, 48.5 mmol) were added, and the mixture was stirred for 5.5 hours under heating to reflux. To the reaction solution, iron powder (9.0 g, 161 mmol) was then further added, and the mixture was further stirred for 2 hours under heating to reflux. The mixture was allowed to cool, then diluted with a saturated aqueous solution of sodium bicarbonate and ethyl acetate, and filtered to remove insoluble matter. From the filtrate, the organic solvent was distilled off under reduced pressure, followed by extraction with ethyl acetate from the aqueous layer. The organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate. Then, the solvent was distilled off under reduced pressure, and the residue was purified by amino column chromatography to obtain the compound of interest as a pale yellow oil (5.5 g).

Workup

  1. temperatureunder heating to reflux
  2. stirringthe mixture was further stirred for 2 hours
  3. temperatureunder heating to reflux
  4. temperatureto cool
  5. filtrationfiltered
  6. customto remove insoluble matter
  7. distillationFrom the filtrate, the organic solvent was distilled off under reduced pressure
  8. extractionfollowed by extraction with ethyl acetate from the aqueous layer
  9. washThe organic layer was washed with saturated saline
  10. dry with materialdried over anhydrous magnesium sulfate
  11. distillationThen, the solvent was distilled off under reduced pressure
  12. customthe residue was purified by amino column chromatography

Sources & evidence

ORD record
ord-d71629e24f2d4e5998e2723b6e46d6e1
Source dataset
uspto-grants-2011_05
Patent number
US07947738B2

Reaction notes

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