1,1-Dimethylethyl (3S)-4-azido-3-[(3-chloro-4-cyanophenyl)amino]butanoate → 1,1-Dimethylethyl (3S)-4-amino-3-[(3-chloro-4-cyanophenyl)amino]butanoate

HRID 1160393Notes

Reaction equation

HRID 1160393 reaction equation
[N:1]([CH2:4][C@@H:5]([NH:14][C:15]1[CH:20]=[CH:19][C:18]([C:21]#[N:22])=[C:17]([Cl:23])[CH:16]=1)[CH2:6][C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])=[N+]=[N-]>CCO.O=[Pt]=O>[NH2:1][CH2:4][C@@H:5]([NH:14][C:15]1[CH:20]=[CH:19][C:18]([C:21]#[N:22])=[C:17]([Cl:23])[CH:16]=1)[CH2:6][C:7]([O:9][C:10]([CH3:11])([CH3:13])[CH3:12])=[O:8]

Participants

4

Reactant 1

HCID 866183611,1-Dimethylethyl (3S)-4-azido-3-[(3-chloro-4-cyanophenyl)amino]butanoate

Product 1

HCID 595161531,1-Dimethylethyl (3S)-4-amino-3-[(3-chloro-4-cyanophenyl)amino]butanoateYield 84.1%

Reagents, catalysts & solvents 2

HCID 345198Adams' catalystCatalystHCID 702EthanolSolvent2×

Procedure

PtO2 (0.98 g) in EtOH (100 mL) was reduced with H2 (40 psi) on a Parr shaker for 20 minutes. To this mixture was added a solution of 1,1-dimethylethyl (3S)-4-azido-3-[(3-chloro-4-cyanophenyl)amino]butanoate (25.5 g, 76 mmol) in EtOH (100 mL) and the reaction was shaken on a Parr shaker under H2 (35 psi) for 2.5 h. The reaction mixture was filtered through a pad Celite and concentrated. The residue was dissolved in CH2Cl2, washed with H2O, dried over MgSO4, filtered and the solvent removed. The residue was triturated with Et2O (75 mL), chilled, and filtered to afford the titled product (19.8 g, 84%). 1H-NMR (CD3OD) δ: 1.39 (9H, s), 2.39 (1H, m), 2.58 (1H, m), 2.73 (1H, m), 2.79 (1H, m), 3.97 (1H, m), 6.68 (1H, d, J=8 Hz), 6.84 (1H, s), 7.44 (1H, d, J=8.8 Hz). LC-MS (ES) m/e 310.6 (M+H)+.

Workup

  1. filtrationThe reaction mixture was filtered through a pad Celite
  2. concentrationconcentrated
  3. dissolutionThe residue was dissolved in CH2Cl2
  4. washwashed with H2O
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. customthe solvent removed
  8. customThe residue was triturated with Et2O (75 mL)
  9. temperaturechilled
  10. filtrationfiltered

Sources & evidence

ORD record
ord-5e7d05d288164c9082d295bd102ef399
Source dataset
uspto-grants-2010_10
Patent number
US07816395B2

Reaction notes

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