Hydrogen Peroxide → 1,1-Dimethylethyl (2S)-2-[[[(1,1-dimethylethyl)dimethylsilyl]oxy]methyl]-2,5-dihydro-5-oxo-1H-pyrrole-1-carboxylate

HRID 1662092Notes

Reaction equation

HRID 1662092 reaction equation
C[Si]([N-][Si](C)(C)C)(C)C.[Na+].[Si:11]([O:18][CH2:19][C@@H:20]1[CH2:24][CH2:23][C:22](=[O:25])[N:21]1[C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])([C:14]([CH3:17])([CH3:16])[CH3:15])([CH3:13])[CH3:12].C1([Se]Cl)C=CC=CC=1.OO>C1COCC1.CN1C(=O)N(C)CCC1>[Si:11]([O:18][CH2:19][C@@H:20]1[CH:24]=[CH:23][C:22](=[O:25])[N:21]1[C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])([C:14]([CH3:17])([CH3:16])[CH3:15])([CH3:13])[CH3:12]

Participants

7

Reactant 4

HCID 784Hydrogen PeroxideHCID 21928ChloroselenobenzeneHCID 2724254Sodium bis(trimethylsilyl)amideHCID 109036131,1-Dimethylethyl (2S)-2-[[[(1,1-dimethylethyl)dimethylsilyl]oxy]methyl]-5-oxo-1-pyrrolidinecarboxylate

Product 1

HCID 108711501,1-Dimethylethyl (2S)-2-[[[(1,1-dimethylethyl)dimethylsilyl]oxy]methyl]-2,5-dihydro-5-oxo-1H-pyrrole-1-carboxylate

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent3×HCID 816462(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl-Solvent

Conditions

Temperature
-78 °C

Procedure

To a solution of NaHMDS (35 mL, 35 mmol, 1.0M solution in THF) in THF (45 mL) at 0° C. was added DMPU (4.8 mL) and the reaction mixture was stirred 20 minutes. The reaction mixture was cooled to −78° C. and to it was added a solution of 4-2 (4.8 g, 14.6 mmol) in THF (20 mL) and the reaction was stirred an additional 30 minutes. At this time a solution of phenylselenenyl chloride (3.35 g, 17.5 mmol) in THF (15 mL) was added and the reaction was stirred at −78° C. for 2 h. The reaction quenched with saturated NH4Cl (200 mL) at −78° C. and the reaction mixture was warmed to ambient temperature. The reaction mixture was extracted with EtOAc (3×200 mL) and the combined organic phase was dried over magnesium sulfate and concentrated. The residue was resuspended in THF (100 mL) and cooled to 0° C. To the reaction mixture was added H2O2 (6.4 mL, 73 mmol, 35% solution in water). The reaction mixture was stirred 2 h and quenched with saturated NaHCO3 (200 mL). The reaction was extracted with EtOAc (3×200 mL) and the combined organic phase was dried over magnesium sulfate and concentrated. The residue was purified by normal phase silica gel chromatography (0 to 70% EtOAc in hexanes) to afford the product (4-3) as an off-white solid. ESI+ MS: [M-Boc+H]+ 228.3.

Workup

  1. stirringthe reaction was stirred an additional 30 minutes
  2. stirringthe reaction was stirred at −78° C. for 2 h
  3. customThe reaction quenched with saturated NH4Cl (200 mL) at −78° C.
  4. temperaturethe reaction mixture was warmed to ambient temperature
  5. extractionThe reaction mixture was extracted with EtOAc (3×200 mL)
  6. dry with materialthe combined organic phase was dried over magnesium sulfate
  7. concentrationconcentrated
  8. temperaturecooled to 0° C
  9. stirringThe reaction mixture was stirred 2 h
  10. customquenched with saturated NaHCO3 (200 mL)
  11. extractionThe reaction was extracted with EtOAc (3×200 mL)
  12. dry with materialthe combined organic phase was dried over magnesium sulfate
  13. concentrationconcentrated
  14. customThe residue was purified by normal phase silica gel chromatography (0 to 70% EtOAc in hexanes)

Sources & evidence

ORD record
ord-5481c039c4de4e55aa5cc291e8479914
Source dataset
uspto-grants-2011_10
Patent number
US08030495B2

Reaction notes

Loading…