Sodium Bromide → N-benzyl-N-(tert-butoxycarbonyl)-L-phenylalaninal

HRID 429396Notes

Reaction equation

HRID 429396 reaction equation
[C:1]([O:5][C:6]([N:8]([CH2:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)[C@H:9]([CH2:17][OH:18])[CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].CC1(C)N([O])C(C)(C)CCC1.[Br-].[Na+].C(=O)(O)[O-].[Na+]>C1(C)C=CC=CC=1.O.C(OCC)(=O)C>[C:1]([O:5][C:6]([N:8]([CH2:19][C:20]1[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=1)[C@H:9]([CH:17]=[O:18])[CH2:10][C:11]1[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=1)=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

8

Reactant 4

HCID 253881Sodium BromideHCID 516892Sodium BicarbonateHCID 2724126TempoHCID 15434535N-(t-Butoxycarbonyl)-N-benzyl-L-phenylalaninol

Product 1

HCID 11099858N-benzyl-N-(tert-butoxycarbonyl)-L-phenylalaninalYield 100.3%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 0.32 g(0.94 mmoles) of N-(t-butoxycarbonyl)-N-benzyl-L-phenylalaninol in 2.8 mL of toluene was added 2.4 mg (0.015 mmoles) of 2,2,6,6-tetramethyl-1-piperidinyloxy, free radical (TEMPO), 0.1 g (0.97 mmoles) of sodium bromide, 2.8 mL of ethyl acetate and 0.34 mL of water. The mixture was cooled to 0° C. and an aqueous solution of 4.2 mL of 5% household bleach containing 0.23 g (3.0 mL, 2.738 mmoles) of sodium bicarbonate was added slowly over 30 minutes. The mixture was stirred at 0° C. for 10 minutes. Three more additions (0.4 mL each) of bleach was added followed by stirring for 10 minutes after each addition to consume all the stating material. The two phase mixture was allowed to separate. The aqueous layer was extracted twice with 8 mL of toluene. The combined organic layer was washed with 1.25 mL of a solution containing 0.075 g of potassium iodide, sodium bisulfate(0.125 g) and water(1.1 mL), 1.25 mL of 10% aqueous sodium thiosulfate solution, 1.25 mL of pH 7 phosphate buffer and 1.5 mL of brine solution. The organic solution was dried over magnesium sulfate, filtered and concentrated under reduced pressure to give 0.32 g (100% yield) of N-(t-Butoxycarbonyl)-N-benzyl-L-phenylalaninal.

Workup

  1. additionwas added slowly over 30 minutes
  2. additionThree more additions (0.4 mL each) of bleach was added
  3. stirringby stirring for 10 minutes
  4. additionafter each addition
  5. customto consume all the stating material
  6. customto separate
  7. extractionThe aqueous layer was extracted twice with 8 mL of toluene
  8. washThe combined organic layer was washed with 1.25 mL of a solution
  9. additioncontaining 0.075 g of potassium iodide, sodium bisulfate(0.125 g) and water(1.1 mL), 1.25 mL of 10% aqueous sodium thiosulfate solution, 1.25 mL of pH 7 phosphate buffer and 1.5 mL of brine solution
  10. dry with materialThe organic solution was dried over magnesium sulfate
  11. filtrationfiltered
  12. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-3e34447c5b4f4e23838830f88857aa17
Source dataset
uspto-grants-2001_11
Patent number
US06316496B1

Reaction notes

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