Potassium Carbonate → (S)-3-(4-But-3-enyloxy-phenyl)-2-tert-butoxycarbonylamino-propionic acid methyl ester

HRID 2371309Notes

Reaction equation

HRID 2371309 reaction equation
[CH3:1][O:2][C:3](=[O:21])[C@H:4]([CH2:13][C:14]1[CH:19]=[CH:18][C:17]([OH:20])=[CH:16][CH:15]=1)[NH:5][C:6]([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7].C(=O)([O-])[O-].[K+].[K+].Br[CH2:29][CH2:30][CH:31]=[CH2:32]>CN(C=O)C.CCOC(C)=O>[CH3:1][O:2][C:3](=[O:21])[C@@H:4]([NH:5][C:6]([O:8][C:9]([CH3:12])([CH3:10])[CH3:11])=[O:7])[CH2:13][C:14]1[CH:19]=[CH:18][C:17]([O:20][CH2:32][CH2:31][CH:30]=[CH2:29])=[CH:16][CH:15]=1

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 21241Homoallyl bromideHCID 7019130Boc-Tyr-OMe

Product 1

HCID 66846982(S)-3-(4-But-3-enyloxy-phenyl)-2-tert-butoxycarbonylamino-propionic acid methyl ester

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent2×

Procedure

N—BOC-tyrosine methyl ester (10.0 g, 33.9 mmol) was dissolved in DMF (40 mL) and potassium carbonate (5.62 g, 40.7 mmol) and 4-bromo-1-butene (4.13 mL, 40.7 mmol) were added. The mixture was stirred at rt for 18 h before being diluted with EtOAc (120 mL) and partitioned with 1M hydrochloric acid. The organic phase was washed with hydrochloric acid and then with brine before being dried (MgSO4), filtered and concentrated in vacuo. The crude material was purified by flash chromatography on silica using a gradient of EtOAc and (50/70) petroleum ether to yield a white solid, 3.20 g, 27%. Rf=0.82 (1/2 EtOAc/(50/70) petroleum ether).

Workup

  1. custompartitioned with 1M hydrochloric acid
  2. washThe organic phase was washed with hydrochloric acid
  3. dry with materialwith brine before being dried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe crude material was purified by flash chromatography on silica using a gradient of EtOAc and (50/70) petroleum ether
  7. customto yield a white solid, 3.20 g, 27%

Sources & evidence

ORD record
ord-3a366d208f34404e8eaf4834487c0031
Source dataset
uspto-grants-2014_04
Patent number
US08710178B2

Reaction notes

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