(3S,4R)-3-[(R)-1-hydroxyethyl]-4-[(R)-1-methyl-3-diazo-3-allyloxycarbonyl-2-oxopropyl]-2-azetidinone → allyl (4R,5R,6S)-6-[(1R)-1-hydroxyethyl]-4-methyl-3,7-dioxo-1-azabicyclo[3.2.0]heptane-2-carboxylate

HRID 346383

Reaction equation

HRID 346383 reaction equation
[N+](=[C:3]([C:10](=[O:21])[C@@H:11]([C@@H:13]1[C@@H:16]([C@H:17]([OH:19])[CH3:18])[C:15](=[O:20])[NH:14]1)[CH3:12])[C:4]([O:6][CH2:7][CH:8]=[CH2:9])=[O:5])=[N-]>ClCCl.C(#N)C.C([O-])(=O)CCCCCCC.[Rh+2].C([O-])(=O)CCCCCCC>[OH:19][C@@H:17]([C@H:16]1[C:15](=[O:20])[N:14]2[C@@H:13]1[C@@H:11]([CH3:12])[C:10](=[O:21])[CH:3]2[C:4]([O:6][CH2:7][CH:8]=[CH2:9])=[O:5])[CH3:18]

Participants

5

Reactant 1

HCID 54331596(3S,4R)-3-[(R)-1-hydroxyethyl]-4-[(R)-1-methyl-3-diazo-3-allyloxycarbonyl-2-oxopropyl]-2-azetidinone

Product 1

HCID 14329061allyl (4R,5R,6S)-6-[(1R)-1-hydroxyethyl]-4-methyl-3,7-dioxo-1-azabicyclo[3.2.0]heptane-2-carboxylate

Reagents, catalysts & solvents 3

HCID 10178397Rhodium(II) octanoateCatalyst2×HCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of allyl (4R)-2-diazo-4-[(2R,3S)-3-{(1R)-1-hydroxyethyl}-4-oxoazetidin-2-yl]-3-oxopentanoate (0.36 g) in dichloromethane (2.25 ml) was added rhodium(II) octanoate (6 mg) under reflux. After refluxing for 20 minutes, to the solution was added rhodium(II) octanoate (6 mg). The mixture was refluxed for 40 minutes. The reaction mixture was cooled and evaporated in vacuo to give a residue. The residue was dissolved in anhydrous acetonitrile (4.5 ml) and then evaporated. This operation was repeated once again and the resulting residue was dried in vacuo to give allyl (4R,5R,6S)-6-[(1R)-1-hydroxyethyl]-4-methyl-3,7-dioxo-1-azabicyclo[3.2.0]heptane-2-carboxylate. The residue containing the compound obtained above was dissolved in anhydrous acetonitrile (4.5 ml) and cooled to 0°-5° C. under an atmosphere of nitrogen. To this solution were added diphenyl phosphorochloridate (0.35 ml) and N,N-diisopropyl-N-ethylamine (0.32 ml) successively and the solution was stirred at 0°-5° C. for 1 hour. To the resulting solution were added dropwise a solution of (2S,4S)-1-allyloxycarbonyl-4-mercapto-2-[(ureidocarbonylxethyl)oxymethyl]pyrrolidine (0.35 g) in a mixture of dimethylformamide (1 ml) and acetonitrile (3 ml), and N,N-diisopropyl-N-ethylamine (0.35 ml) successively with stirring at 0°-5° C., and the stirring was continued at the same temperature for 3 hours. To a reaction mixture was added ethyl acetate (50 ml) and water (50 ml) with stirring, and the organic layer was separated.

Workup

  1. temperatureunder reflux
  2. temperatureAfter refluxing for 20 minutes, to the solution
  3. temperatureThe mixture was refluxed for 40 minutes
  4. temperatureThe reaction mixture was cooled
  5. customevaporated in vacuo
  6. customto give a residue
  7. customevaporated
  8. customthe resulting residue was dried in vacuo

Sources & evidence

ORD record
ord-eea6bb657acc4fbba48816ed29cf72ff
Source dataset
uspto-grants-1991_10
Patent number
US05061804

Linked notes

Loading…