Triethylamine → Methyl (S)-3-(1-((tert-butoxycarbonyl)amino)ethyl)benzoate

HRID 64432Notes

Reaction equation

HRID 64432 reaction equation
[C:1]([O:5][C:6](=[O:17])[NH:7][C@H:8]([C:10]1[CH:15]=[CH:14][CH:13]=[C:12](Br)[CH:11]=1)[CH3:9])([CH3:4])([CH3:3])[CH3:2].C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(N(CC)CC)C.[C]=O>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(OCC)(=O)C.O.CO.CN(C=O)C>[C:1]([O:5][C:6]([NH:7][C@H:8]([C:10]1[CH:11]=[C:12]([CH:13]=[CH:14][CH:15]=1)[C:6]([O:5][CH3:1])=[O:17])[CH3:9])=[O:17])([CH3:4])([CH3:3])[CH3:2]

Participants

10

Reactant 4

HCID 8471TriethylamineHCID 812191,3-Bis(diphenylphosphino)propane2×HCID 56971804(S)-N-Boc-1-(3-bromophenyl)ethylamineHCID 178418416HCID 178418416, compound

Product 1

HCID 86713444Methyl (S)-3-(1-((tert-butoxycarbonyl)amino)ethyl)benzoateYield 151.2%

Reagents, catalysts & solvents 5

HCID 167845palladium(II) acetateCatalyst2×HCID 887MethanolSolventHCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

To 820 mg of tert-butyl[(1S)-1-(3-bromophenyl)ethyl]carbamate were added 113 mg of 1,3-bis(diphenylphosphino)propane, 62 mg of palladium acetate, 0.84 ml of triethylamine, 8 ml of DMF, and 12 ml of methanol, followed by stirring at room temperature for 1 hour. While stirring at room temperature, carbon monooxide was intaken for 10 minutes, followed by stirring at 80° C. overnight under a carbon monooxide atmosphere. 113 mg of 1,3-bis(diphenylphosphino)propane and 62 mg of palladium acetate were added thereto, followed by stirring at 80° C. overnight. To the reaction mixture were added water and ethyl acetate to carry out a layer separation operation. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 577 mg of methyl 3-{(1S)-1-[(tert-butoxycarbonyl)amino]ethyl}benzoate.

Workup

  1. stirringWhile stirring at room temperature
  2. stirringby stirring at 80° C. overnight under a carbon monooxide atmosphere
  3. stirringby stirring at 80° C. overnight
  4. customa layer separation operation
  5. washThe organic layer was washed with saturated brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. customthe solvent was evaporated under reduced pressure
  8. customThe obtained residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-883b23c1c5814e0b8408008803b23aa6
Source dataset
uspto-grants-2016_09
Patent number
US09447090B2

Reaction notes

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