Ammonium formate → HCID 10176280, compound

HRID 892093Notes

Reaction equation

HRID 892093 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].C(OC([NH:18][C@H:19]([CH2:24][C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)[CH2:20][C:21](O)=[O:22])=O)(=O)C1C=CC=CC=1.C(OC(N[C@H](CC1C=CC=CC=1)CCO)=O)C1C=CC=CC=1.C([O-])=O.[NH4+]>O1CCCC1.CO.[OH-].[OH-].[Pd+2].O.C(OCC)(=O)C>[NH2:18][C@H:19]([CH2:24][C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)[CH2:20][CH2:21][OH:22]

Participants

10

Reactant 4

HCID 2723923Ammonium formateHCID 21226445Aluminium lithium hydride2×HCID 69662162HCID 69662162, compoundHCID 86589631HCID 86589631, compound

Product 1

HCID 10176280HCID 10176280, compoundYield 87%

Reagents, catalysts & solvents 5

HCID 9942167Palladium hydroxideCatalystHCID 887MethanolSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

To a solution (70 mL) of lithium aluminum hydride (1.50 g, 39.5 mmol, 3.0 equivalents) in tetrahydrofuran was added dropwise a solution of (R)-N-(benzoyloxy-carbonyl)-3-amino-4-phenylbutanoic acid (4.84 g, 13.1 mmol), which was obtained by the method described in Tetrahedron, 44, p. 5525, 1988 and Journal of Organic Chemistry (J. Org. Chem.), 64, p. 6411, 1999, in tetrahydrofuran (30 mL) under ice cooling, and the mixture was stirred at room temperature for 30 minutes. After the reaction solution was cooled on ice, excess lithium aluminum hydride was decomposed with ethyl acetate and water. The deposited solid was removed by filtration using a filtration aid, and the filtrate was extracted with chloroform. The organic layer was washed with saturated aqueous sodium chloride and dried over anhydrous sodium sulfate, and the solvent was evaporated. After the resulting residue was purified by silica gel column chromatography (ethyl acetate:n-hexane=50:50), the resulting (R)-N-(benzyloxycarbonyl)-3-amino-4-phenyl-1-butanol (1.37 g, 5.09 mmol) was dissolved in methanol (30 mL), and to the solution were added 20% palladium hydroxide/carbon (200 mg) and ammonium formate (1.30 g, 20.6 mmol, 4.1 equivalents), and then the mixture was stirred for 1 hour with heating. After the catalyst was removed by using a filtration aid, the solvent was evaporated. To the residue was added ethyl acetate, and the deposited solid was collected by filtration to obtain the title compound (730 mg, 87%).

Workup

  1. customwhich was obtained by the method
  2. customThe deposited solid was removed by filtration
  3. extractionthe filtrate was extracted with chloroform
  4. washThe organic layer was washed with saturated aqueous sodium chloride
  5. dry with materialdried over anhydrous sodium sulfate
  6. customthe solvent was evaporated
  7. customAfter the resulting residue was purified by silica gel column chromatography (ethyl acetate:n-hexane=50:50)
  8. temperaturewith heating
  9. customAfter the catalyst was removed
  10. customthe solvent was evaporated
  11. additionTo the residue was added ethyl acetate
  12. filtrationthe deposited solid was collected by filtration

Sources & evidence

ORD record
ord-b6626e67bf8f4e8fa863bc0a6baa4a42
Source dataset
uspto-grants-2006_02
Patent number
US07005430B2

Reaction notes

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