Sodium borohydride → (S)-tert-Butyl (1-methyl-5-oxopyrrolidin-3-yl)carbamate

HRID 1160401Notes

Reaction equation

HRID 1160401 reaction equation
[BH4-].[Na+].[CH3:3][C:4]([O:7][C:8]([NH:10][C@H:11]([C:23]([NH:25][CH3:26])=S)[CH2:12][C:13](OCC1C=CC=CC=1)=[O:14])=[O:9])([CH3:6])[CH3:5]>C1COCC1.CCO>[CH3:26][N:25]1[C:13](=[O:14])[CH2:12][C@H:11]([NH:10][C:8](=[O:9])[O:7][C:4]([CH3:6])([CH3:5])[CH3:3])[CH2:23]1

Participants

5

Reactant 2

HCID 4311764Sodium borohydrideHCID 59516226Phenylmethyl (3S)-3-({[(1,1-dimethylethyl)oxy]carbonyl}amino)-4-(methylamino)-4-thioxobutanoate

Product 1

HCID 45092180(S)-tert-Butyl (1-methyl-5-oxopyrrolidin-3-yl)carbamateYield 48%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

NaBH4 (2.7 g, 74.23 mmol) was added portionwise to an ice cold solution of phenylmethyl (3S)-3-({[(1,1-dimethylethyl)oxy]carbonyl}amino)-4-(methylamino)-4-thioxobutanoate (3.3 g, 9.36 mmol) and NiCl2.6H2O (5.1 g, 21.62 mmol) in THF (50 mL) and EtOH (50 mL) and the reaction mixture was stirred at room temperature for 2.5 days. The resulted black mixture was then filtered through a pad of Celite and the filtrate was concentrated. To this residue was added toluene (15 mL) and the solution was refluxed for 12 h. After cooling to room temperature, the reaction was concentrated and purified via silica gel chromatography with 0% MeOH in CH2Cl2 grading to 10% MeOH in CH2Cl2 to give the titled product (0.96 g, 48%) as a white solid. 1H-NMR (CDCl3) δ: 1.466 (9H, s), 2.270 (1H, dd, J=16 Hz, 4 Hz), 2.770 (1H, m), 2.874 (3H, s), 3.260 (1H, dd, J=8 Hz, 4 Hz), 3.720 (1H, m), 4.310 (1H, s), 4.820 (1H, s). LC-MS (ES) m/e 215.2 (M+H)+.

Workup

  1. filtrationThe resulted black mixture was then filtered through a pad of Celite
  2. concentrationthe filtrate was concentrated
  3. additionTo this residue was added toluene (15 mL)
  4. temperaturethe solution was refluxed for 12 h
  5. temperatureAfter cooling to room temperature
  6. concentrationthe reaction was concentrated
  7. custompurified via silica gel chromatography with 0% MeOH in CH2Cl2 grading to 10% MeOH in CH2Cl2

Sources & evidence

ORD record
ord-a1165b8e86324fd58d0c8168255a77f9
Source dataset
uspto-grants-2010_10
Patent number
US07816395B2

Reaction notes

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