Carbon Dioxide → ethyl (S)-2-tert-butoxycarbonylamino-3-(4-but-2-ynyloxy-phenyl)-propionate

HRID 1779195Notes

Reaction equation

HRID 1779195 reaction equation
[CH2:1]([O:3][C:4](=[O:22])[C@H:5]([CH2:14][C:15]1[CH:20]=[CH:19][C:18]([OH:21])=[CH:17][CH:16]=1)[NH:6][C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])[CH3:2].C(=O)([O-])[O-].[K+].[K+].Br[CH2:30][C:31]#[C:32][CH3:33].[Cl-].[NH4+].C(=O)=O>CN(C=O)C>[C:10]([O:9][C:7]([NH:6][C@@H:5]([CH2:14][C:15]1[CH:20]=[CH:19][C:18]([O:21][CH2:30][C:31]#[C:32][CH3:33])=[CH:17][CH:16]=1)[C:4]([O:3][CH2:1][CH3:2])=[O:22])=[O:8])([CH3:13])([CH3:11])[CH3:12]

Participants

7

Reactant 5

HCID 280Carbon DioxideHCID 11430Potassium CarbonateHCID 25517Ammonium ChlorideHCID 27568621-Bromo-2-butyneHCID 11077750Ethyl N-(tert-butoxycarbonyl)-L-tyrosinate

Product 1

HCID 90060290ethyl (S)-2-tert-butoxycarbonylamino-3-(4-but-2-ynyloxy-phenyl)-propionateYield 96.2%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

In dehydrated DMF (5.0 mL) was dissolved 1.35 g (4.23 mmol) of Boc-L-tyrosine ethyl ester (AK Scientific, Inc catalogue No 71054), and anhydrous potassium carbonate (0.7 g, 5.08 mmol) and 1-bromo-2-butyne (0.619 g, 4.65 mmol) were added at room temperature. The mixture was stirred under argon atmosphere for 21 hours. Subsequently, a saturated aqueous solution of ammonium chloride was added to the reaction solution until generation of carbon dioxide gas stopped. This reaction solution was extracted with ethyl acetate, and washed with water and a saturated brine in this order. The extracted organic layer was dried over anhydrous sodium sulfate. The solvent was then distilled off under reduced pressure. The obtained oily residue was purified by silica gel chromatography (20 g cartridge was used) using 10% ethyl acetate/n-hexane as an elution solvent to obtain 1.47 g (92% yield) of the title compound as clear and colorless oil.

Workup

  1. additionwere added at room temperature
  2. extractionThis reaction solution was extracted with ethyl acetate
  3. washwashed with water
  4. dry with materialThe extracted organic layer was dried over anhydrous sodium sulfate
  5. distillationThe solvent was then distilled off under reduced pressure
  6. customThe obtained oily residue was purified by silica gel chromatography (20 g cartridge was used)

Sources & evidence

ORD record
ord-3dc25f3e4aaa4892bad5e2e12fd4aaa2
Source dataset
uspto-grants-2016_02
Patent number
US09266853B2

Reaction notes

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