Diazomethane → HCID 86585257, compound

HRID 1280084Notes

Reaction equation

HRID 1280084 reaction equation
[C:1]([NH:8][C@H:9]([C:25](O)=[O:26])[CH2:10][C:11]1[CH:16]=[CH:15][C:14]([O:17][C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])=[CH:13][CH:12]=1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].ClC(OCC(C)C)=O.CCN(C(C)C)C(C)C.[N+:45](=[CH2:47])=[N-:46]>C1COCC1.CCOCC>[C:21]([O:20][C:18](=[O:19])[O:17][C:14]1[CH:13]=[CH:12][C:11]([CH2:10][C@H:9]([NH:8][C:1]([O:3][C:4]([CH3:6])([CH3:7])[CH3:5])=[O:2])[C:25](=[O:26])[CH:47]=[N+:45]=[N-:46])=[CH:16][CH:15]=1)([CH3:22])([CH3:24])[CH3:23]

Participants

7

Reactant 4

HCID 9550DiazomethaneHCID 62365Isobutyl chloroformate2×HCID 81531DiisopropylethylamineHCID 7010630BOC-TYR(BOC)-OH

Product 1

HCID 86585257HCID 86585257, compound

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

N,O-Bis-Boc-(S)-tyrosine (6.00 g, 15.73 mmol) was dissolved in THF (40 mL), the solution stirred under an argon atmosphere and cooled in an ice bath. Isobutyl chloroformate (3.0 6mL, 23.59 mmol) was added followed by DIEA (8.22 mL, 47.19 mmol). Additional isobutyl chloroformate (1 mL) was added after 1.5 and 2.5 h. To the cold suspension was then added a ca 0.6M Et2O solution of diazomethane (80 mL) by portions. After 15 min. of stirring, nitrogen was diffused in the solution for 0.5 hr. The solvent was evaporated, the residue taken into EtOAc (75 ml) and the solution washed with 0.5M aqueous citric acid (2×50 mL), 5% aqueous sodium bicarbonate (2×50 mL) and brine (50 mL). After drying (MgSO4) and evaporation of the solvent under reduced pressure, the residue was purified by flash chromatography (20% EtOAc/hexane) to give the title compound (5.52 g) of a yellowish solid.

Workup

  1. temperaturecooled in an ice bath
  2. stirringAfter 15 min. of stirring
  3. customThe solvent was evaporated
  4. washthe solution washed with 0.5M aqueous citric acid (2×50 mL), 5% aqueous sodium bicarbonate (2×50 mL) and brine (50 mL)
  5. customAfter drying
  6. custom(MgSO4) and evaporation of the solvent under reduced pressure
  7. customthe residue was purified by flash chromatography (20% EtOAc/hexane)

Sources & evidence

ORD record
ord-84e683bf368a40309fd5fa69c4d80b77
Source dataset
uspto-grants-2002_09
Patent number
US06448281B1

Reaction notes

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