Hydrogen Peroxide → di-tert-butyl 4-(3-hydroxypropyl)-N-trityl-L-glutamate

HRID 1466546Notes

Reaction equation

HRID 1466546 reaction equation
[CH2:1]([CH:4]([C:34]([O:36][C:37]([CH3:40])([CH3:39])[CH3:38])=[O:35])[CH2:5][C@@H:6]([C:27]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:28])[NH:7][C:8]([C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)([C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)[CH:2]=[CH2:3].[OH-:41].[Na+].OO.O>C1COCC1>[OH:41][CH2:3][CH2:2][CH2:1][CH:4]([C:34]([O:36][C:37]([CH3:40])([CH3:39])[CH3:38])=[O:35])[CH2:5][C@@H:6]([C:27]([O:29][C:30]([CH3:31])([CH3:32])[CH3:33])=[O:28])[NH:7][C:8]([C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)([C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)[C:15]1[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=1

Participants

6

Reactant 4

HCID 784Hydrogen PeroxideHCID 962WaterHCID 14798Sodium HydroxideHCID 86731832di-tert-butyl 4-allyl-N-trityl-L-glutamate

Product 1

HCID 86731833di-tert-butyl 4-(3-hydroxypropyl)-N-trityl-L-glutamateYield 44%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

Borane tetrahydrofuran complex (1M, 2.8 mL, 2.8 mmol) was added drop wise to a solution of di-tert-butyl 4-allyl-N-trityl-L-glutamate (1.00 g, 1.85 mmol) in THF (10 mL) at 0° C. The resulting mixture was stirred for 2 h at 0° C. and for 16 h at room temperature. The solution was cooled to 0° C. NaOH (1M, 3 mL) and H2O2 (30% in water, 3 mL) were added drop wise. The mixture was stirred at 0° C. for 1 h. Water (5 mL) was added and the mixture was concentrated under reduced pressure. The aqueous residue was extracted with ethyl acetate. The combined organic fraction was washed with brine, dried over sodium sulfate, filtrated and concentrated. The crude product was purified by flash chromatography (silica, ethyl acetate/hexane) to afford di-tert-butyl 4-(3-hydroxypropyl)-N-trityl-L-glutamate (0.46 g, 44%) as a mixture of (4S,4S)/(2S,4R) diastereoisomers.

Workup

  1. temperatureThe solution was cooled to 0° C
  2. stirringThe mixture was stirred at 0° C. for 1 h
  3. concentrationthe mixture was concentrated under reduced pressure
  4. extractionThe aqueous residue was extracted with ethyl acetate
  5. washThe combined organic fraction was washed with brine
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltrated
  8. concentrationconcentrated
  9. customThe crude product was purified by flash chromatography (silica, ethyl acetate/hexane)

Sources & evidence

ORD record
ord-fb8543b2eb144ebf89ce6ae3d9129c29
Source dataset
uspto-grants-2015_04
Patent number
US09000037B2

Reaction notes

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