Hydrochloric Acid → Methyl 3-oxo-4-{4-[(trityloxy)methyl]-2-cyclopenten-1-yl}-3,4-dihydro-2-pyrazinecarboxylate

HRID 392307Notes

Reaction equation

HRID 392307 reaction equation
[O:1]=[C:2]1[NH:7][CH:6]=[CH:5][N:4]=[C:3]1[C:8]([O:10][CH3:11])=[O:9].[H-].[Na+].C(O[CH:18]1[CH2:22][CH:21]([CH2:23][O:24][C:25]([C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)([C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)[C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[CH:20]=[CH:19]1)(=O)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.Cl>CN(C)C=O.O1CCCC1.C(OCC)(=O)C.O>[O:1]=[C:2]1[N:7]([CH:18]2[CH2:22][CH:21]([CH2:23][O:24][C:25]([C:38]3[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=3)([C:26]3[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=3)[C:32]3[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=3)[CH:20]=[CH:19]2)[CH:6]=[CH:5][N:4]=[C:3]1[C:8]([O:10][CH3:11])=[O:9]

Participants

10

Reactant 5

HCID 313Hydrochloric AcidHCID 11776TriphenylphosphineHCID 24758Sodium hydrideHCID 1514283Methyl 3-hydroxypyrazine-2-carboxylateHCID 156748174-[(Trityloxy)methyl]-2-cyclopenten-1-yl acetate

Product 1

HCID 22662838Methyl 3-oxo-4-{4-[(trityloxy)methyl]-2-cyclopenten-1-yl}-3,4-dihydro-2-pyrazinecarboxylateYield 37.2%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

In 4.0 mL of N,N-dimethylformamide was dissolved 0.39 g of methyl 3-oxo-3,4-dihydro-2-pyrazinecarboxylate. In an atmosphere of nitrogen gas, 90 mg of sodium hydride was added and stirred at room temperature for 2 hours. Then, a suspension of 0.50 g of 4-[(trityloxy)methyl]-2-cyclopenten-1-yl acetate, 0.62 g of tetrakis-triphenylphosphine palladium and 50 mg of triphenylphosphine in 4 mL of tetrahydrofuran was added, and the mixture thus obtained was stirred at room temperature for one hour and thereafter at 60° C. for 4 hours. The reaction mixture was allowed to cool, diluted with 30 mL of ethyl acetate and 20 mL of water, adjusted to pH 4 with 1 mol/L hydrochloric acid, and separated into layers. The organic layer was washed successively with saturated aqueous solution of sodium hydrogen carbonate, water and saturated aqueous solution of sodium chloride and dried on anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The residue was purified by column chromatography [eluent: hexane:ethyl acetate=1:1] to obtain 0.23 g of methyl 3-oxo-4-{4-[(trityloxy)methyl]-2-cyclopenten-1-yl}-3,4-dihydro-2-pyrazinecarboxylate as a light yellow oily product.

Workup

  1. additionwas added
  2. customthe mixture thus obtained
  3. stirringwas stirred at room temperature for one hour
  4. waitat 60° C. for 4 hours
  5. temperatureto cool
  6. customseparated into layers
  7. washThe organic layer was washed successively with saturated aqueous solution of sodium hydrogen carbonate, water and saturated aqueous solution of sodium chloride
  8. dry with materialdried on anhydrous magnesium sulfate
  9. customthe solvent was removed under reduced pressure
  10. customThe residue was purified by column chromatography [eluent: hexane:ethyl acetate=1:1]

Sources & evidence

ORD record
ord-865ec5d47a36414e8f7a837dc40c236b
Source dataset
uspto-grants-2004_10
Patent number
US06800629B2

Reaction notes

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