(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 1088998

反応式

HRID 1088998 の反応式
[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]

参加物

5

反応物 1

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

生成物 1

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

試薬・触媒・溶媒 3

HCID 10178397Rhodium(II) octanoate触媒2 回HCID 6342Acetonitrile溶媒HCID 6344Dichloromethane溶媒

実験手順

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-[(ureidocarbonylmethyl)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.

後処理

  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

出典と根拠

ORDレコード
ord-80872ea51147426f923bb4baea2d19c7
出典データセット
uspto-grants-1990_10
特許番号
US04963543

関連ノート

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