Pyridine → HCID 86596176, compound

HRID 1271108Notes

Reaction equation

HRID 1271108 reaction equation
[OH:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH2:14][C@H:13]3[N:10]([C:11](=[O:25])[C@@H:12]3[C@H:15]([O:17][Si:18]([CH2:23][CH3:24])([CH2:21][CH3:22])[CH2:19][CH3:20])[CH3:16])[C:9]=2[C:26]([O:28][CH2:29][C:30]2[CH:35]=[CH:34][C:33]([N+:36]([O-:38])=[O:37])=[CH:32][CH:31]=2)=[O:27])=[CH:4][CH:3]=1.N1C=CC=CC=1.ClC(Cl)(Cl)[C:47]([N:49]=C=O)=[O:48].C(OCC)(=O)C>ClCCl>[NH2:49][C:47]([O:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH2:14][C@H:13]3[N:10]([C:11](=[O:25])[C@@H:12]3[C@H:15]([O:17][Si:18]([CH2:23][CH3:24])([CH2:21][CH3:22])[CH2:19][CH3:20])[CH3:16])[C:9]=2[C:26]([O:28][CH2:29][C:30]2[CH:35]=[CH:34][C:33]([N+:36]([O-:38])=[O:37])=[CH:32][CH:31]=2)=[O:27])=[CH:4][CH:3]=1)=[O:48]

Participants

6

Reactant 4

HCID 1049PyridineHCID 8857Ethyl AcetateHCID 76400Trichloroacetyl isocyanateHCID 86596177HCID 86596177, compound

Product 1

HCID 86596176HCID 86596176, compoundYield 52.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

4-Nitrobenzyl (5R,6S)-3-(4-hydroxyphenyl)-7-oxo-6-{(1R)-1-[(triethylsilyl)oxy]ethyl}-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate (200 mg) prepared in the above step was dissolved in dichloromethane (4.5 ml). Thereto were added under ice cooling pyridine in a catalytic amount and trichloroacetyl isocyanate (106 mg), and the mixture was stirred for 1 hour. The reaction mixture was poured into a mixture of ice water and ethyl acetate. The mixture was extracted and separated with a separating funnel. The organic layer was washed with cold water (twice) and a cold saturated aqueous sodium chloride solution in the order, and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure. The residue was dissolved in methanol (13.5 ml) and thereto silica gel (2.7 g) was added. The mixture was stirred for 1.5 hours and then, kept in a refrigerator overnight. After the reaction mixture was diluted with chloroform, silica gel was removed by filtration. The solution was washed with chloroform/methanol (=4/1) and the solvent was removed under reduced pressure. The residue was purified by silica gel thin layer chromatography (chloroform/acetone=9/1) to give 4-nitrobenzyl (5R,6S)-3-{4-[(aminocarbonyl)oxy]phenyl}-6-{(1R)-1-[(triethylsilyl)oxy]ethyl}-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate (113 mg).

Workup

  1. additionThereto were added under ice
  2. extractionThe mixture was extracted
  3. customseparated with a separating funnel
  4. washThe organic layer was washed with cold water (twice) and a cold saturated aqueous sodium chloride solution in the order
  5. dry with materialdried over anhydrous sodium sulfate
  6. customThe solvent was removed under reduced pressure
  7. dissolutionThe residue was dissolved in methanol (13.5 ml)
  8. additionsilica gel (2.7 g) was added
  9. stirringThe mixture was stirred for 1.5 hours
  10. customkept in a refrigerator overnight
  11. additionAfter the reaction mixture was diluted with chloroform, silica gel
  12. customwas removed by filtration
  13. washThe solution was washed with chloroform/methanol (=4/1)
  14. customthe solvent was removed under reduced pressure
  15. customThe residue was purified by silica gel thin layer chromatography (chloroform/acetone=9/1)

Sources & evidence

ORD record
ord-911473e980a14cd38bdee99c3a785d52
Source dataset
uspto-grants-2007_04
Patent number
US07205291B2

Reaction notes

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