Butyl vinyl ether → Ethyl 6-acetyl-8-(benzyloxy)-2-methyl-1-oxo-1,2,3,4-tetrahydro-pyrrolo[1,2-a]-pyrazine-7-carboxylate

HRID 494093

Reaction equation

HRID 494093 reaction equation
[CH2:1]([O:8][C:9]1[C:10]([C:21]([O:23][CH2:24][CH3:25])=[O:22])=[C:11](Br)[N:12]2[CH2:17][CH2:16][N:15]([CH3:18])[C:14](=[O:19])[C:13]=12)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:26]([O-])(=[O:28])[CH3:27].[Tl+].C(N(C(C)C)CC)(C)C.C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(OCCCC)=C>CN(C=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:26]([C:11]1[N:12]2[CH2:17][CH2:16][N:15]([CH3:18])[C:14](=[O:19])[C:13]2=[C:9]([O:8][CH2:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)[C:10]=1[C:21]([O:23][CH2:24][CH3:25])=[O:22])(=[O:28])[CH3:27]

Participants

8

Reactant 5

HCID 8108Butyl vinyl etherHCID 11247thallium(I) acetateHCID 812191,3-Bis(diphenylphosphino)propaneHCID 81531DiisopropylethylamineHCID 68866169Ethyl 8-(benzyloxy)-6-bromo-2-methyl-1-oxo-1,2,3,4-tetrahydro-pyrrolo[1,2-a]-pyrazine-7-carboxylate

Product 1

HCID 68866335Ethyl 6-acetyl-8-(benzyloxy)-2-methyl-1-oxo-1,2,3,4-tetrahydro-pyrrolo[1,2-a]-pyrazine-7-carboxylate

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of ethyl 8-(benzyloxy)-6-bromo-2-methyl-1-oxo-1,2,3,4-tetrahydro-pyrrolo[1,2-a]-pyrazine-7-carboxylate (0.42 g, 1.03 mmol), palladium acetate (29 mg, 0.13 mmol), thallium acetate (0.34 g, 1.29 mmol), diisopropyl ethylamine (0.58 mL, 4.12 mmol), 1,3-bis(diphenylphosphino)propane (60 mg, 0.14 mol), n-butyl vinyl ether (0.67 mL, 5.2 mmol) in DMF (3 mL) was purged with nitrogen for 5 minutes. The mixture was sealed and heated at 100° C. overnight. The reaction mixture was concentrated under vacuum, and the residue was treated with 1 N aq HCl and stirred at room temperature for one hour. The reaction mixture was diluted with dichloromethane. The organic extract was dried over sodium sulfate, filtered and concentrated. The residue was subjected to column chromatography on silica gel eluted with ethyl acetate to provide titled product.

Workup

  1. customwas purged with nitrogen for 5 minutes
  2. customThe mixture was sealed
  3. concentrationThe reaction mixture was concentrated under vacuum
  4. additionthe residue was treated with 1 N aq HCl
  5. additionThe reaction mixture was diluted with dichloromethane
  6. extractionThe organic extract
  7. dry with materialwas dried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated
  10. washeluted with ethyl acetate

Sources & evidence

ORD record
ord-d37487c3c657462abd88c53ff7dd2cf2
Source dataset
uspto-grants-2009_05
Patent number
US07538112B2

Linked notes

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