Ethyl Acetate → HCID 66744319, compound

HRID 1429592Notes

Reaction equation

HRID 1429592 reaction equation
[CH3:1][O:2][C:3](=[O:31])[NH:4][C:5]1[CH:10]=[CH:9][C:8]([C:11]2[O:12][C:13]([C@@H:16]([NH:20][C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])[CH2:17][CH:18]=[CH2:19])=[N:14][N:15]=2)=[C:7]([N+:28]([O-:30])=[O:29])[CH:6]=1.C([O:36]C(N[C@@H](CC=C)C(O)=O)=O)(C)(C)C.CCOC(C)=O>CN(C=O)C>[CH3:1][O:2][C:3](=[O:31])[NH:4][C:5]1[CH:10]=[CH:9][C:8]([C:11]([NH:15][NH:14][C:13](=[O:12])[C@@H:16]([NH:20][C:21]([O:23][C:24]([CH3:26])([CH3:25])[CH3:27])=[O:22])[CH2:17][CH:18]=[CH2:19])=[O:36])=[C:7]([N+:28]([O-:30])=[O:29])[CH:6]=1

Participants

5

Reactant 3

HCID 8857Ethyl AcetateHCID 2734487(2S)-2-(((tert-butoxy)carbonyl)amino)pent-4-enoic acidHCID 67356405HCID 67356405, compound

Product 1

HCID 66744319HCID 66744319, compoundYield 86%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

{4-[5-((S)-1-tert-Butoxycarbonylamino-but-3-enyl)-1,3,4-oxadiazol-2-yl]-3-nitro-phenyl}-carbamic acid methyl ester: 168B (0.3 g, 0.393 mmol) and (S)-2-(tert-butoxycarbonylamino)pent-4-enoic acid (0.085 g, 0.393 mmol) were dissolved in DMF (2 mL) in a 15 mL rbf and TEA (0.274 mL, 1.967 mmol) was added. Mixture was stirred under nitrogen at room temperature while propane phosphonic acid anhydride (T3P), 50% in EtOAc (0.293 mL, 0.983 mmol) was added dropwise. The flask was fitted with a reflux condenser, and the resulting mixture was stirred in an 80° C. oil bath for 5 h. Reaction mixture was poured into ice water and extracted 3× with EtOAc. Combined extracts were washed with sat'd aq. NaHCO3, water and brine, dried over anh. Na2SO4, filtered and evaporated to provide {4-[N′-((S)-2-tert-butoxycarbonylamino-pent-4-enoyl)-hydrazinocarbonyl]-3-nitro-phenyl}-carbamic acid methyl ester, (0.46 g, 86%) as a light yellow solid which was used without further purification. The solid (0.46 g, 1.019 mmol) was dissolved in anhydrous THF (20 mL) under argon and the solution transferred to a 75 mL pressure flask. Burgess reagent (1.33 g, 5.58 mmol) was added, the flask was sealed with a pressure relief cap and then heated in a 75° C. oil bath for 2 h behind a blast shield then left standing overnight at room temperature. Reaction mixture was evaporated on rotary evaporator. Residue was purified by normal phase chromatography to give 168C as a light yellow foam (0.315 g, 71.3%). MS (ESI) m/z: 434.3 (M+H)+ 378.3 (M+H−tBu)+.

Workup

  1. additionwas added
  2. additionwas added dropwise
  3. customThe flask was fitted with a reflux condenser
  4. customReaction mixture
  5. extractionextracted 3× with EtOAc
  6. washCombined extracts were washed with sat'd aq. NaHCO3, water and brine
  7. dry with materialdried over anh. Na2SO4
  8. filtrationfiltered
  9. customevaporated

Sources & evidence

ORD record
ord-264daaa4dd154ef1a7c976bf31e006e8
Source dataset
uspto-grants-2015_01
Patent number
US08940720B2

Reaction notes

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