Water → HCID 57017483、化合物

HRID 703601

反応式

HRID 703601 の反応式
[N+](=[C:3]([C:10](=O)[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-].P(Cl)(OC1C=CC=CC=1)(OC1C=CC=CC=1)=O.[CH2:39]([O:42][C:43]([N:45]1[CH2:49][C@@H:48]([SH:50])[CH2:47][C@H:46]1[CH2:51][O:52][CH2:53][CH2:54][F:55])=[O:44])[CH:40]=[CH2:41].O>C(OCC)(=O)C.C(#N)C.C(N(C(C)C)CC)(C)C.C([O-])(=O)CCCCCCC.[Rh+2].C([O-])(=O)CCCCCCC>[CH2:39]([O:42][C:43]([N:45]1[CH2:49][C@@H:48]([S:50][C:10]2[C@H:11]([CH3:12])[C@H:13]3[N:14]([C:15](=[O:20])[C@@H:16]3[C@H:17]([OH:19])[CH3:18])[C:3]=2[C:4]([O:6][CH2:7][CH:8]=[CH2:9])=[O:5])[CH2:47][C@H:46]1[CH2:51][O:52][CH2:53][CH2:54][F:55])=[O:44])[CH:40]=[CH2:41]

参加物

9

反応物 4

HCID 962WaterHCID 75654Diphenyl chlorophosphateHCID 54331596(3S,4R)-3-[(R)-1-hydroxyethyl]-4-[(R)-1-methyl-3-diazo-3-allyloxycarbonyl-2-oxopropyl]-2-azetidinoneHCID 57241269HCID 57241269、化合物

生成物 1

HCID 57017483HCID 57017483、化合物収率 39.1%

試薬・触媒・溶媒 4

HCID 10178397Rhodium(II) octanoate触媒2 回HCID 6342Acetonitrile溶媒2 回HCID 8857Ethyl Acetate溶媒2 回HCID 81531Diisopropylethylamine溶媒2 回

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 (3.80 g) in ethyl acetate (20 ml) was added rhodium(II) octanoate (20 mg) under reflux in a stream of nitrogen. After 20 minutes, rhodium(II) octanoate (20 mg) was added to the mixture at the same condition. The mixture was refluxed for 40 minutes and concentrated under reduced pressure to give a syrup. The syrup was dissolved in acetonitrile (20 ml) and cooled at 0°-5° C. under atmosphere of nitrogen. To the solution was added diphenyl chlorophosphate (2.94 ml) and N,N-diisopropyl-N-ethylamine (2.69 ml) successively and the mixture was stirred at the same condition for 18 hours. To this mixture were added a solution of (2S,4S)-1-allyloxycarbonyl-2-(2-fluoroethyloxymethyl)-4-mercaptopyrrolidine (3.65 g) in acetonitrile (4 ml) and N,N-diisopropyl-N-ethylamine (2.69 ml) successively at 0°~5° C. The mixture was stirred at 0°-5° C. for one hour and at ambient temperature for 3 hours, and then poured into a mixture of ethyl acetate (100 ml) and water (60 ml). The organic layer was washed with water (60 ml) and brine (60 ml) in turn, dried over magnesium sulfate and concentrated under reduced pressure to give a syrup. The syrup was subjected to a column chromatography on silica gel (60 g) and eluted with a mixture of hexane and ethyl acetate (4:1 V/V) to give allyl (4R,5S,6S)-3-[(2S,4S)-1-allyloxycarbonyl-2-(2-fluoroethyloxymethyl)pyrrolidin-4-yl]thio-6-[(1R)-1-hydroxyethyl]-4-methyl-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate (2.58 g).

後処理

  1. temperatureunder reflux in a stream of nitrogen
  2. temperatureThe mixture was refluxed for 40 minutes
  3. concentrationconcentrated under reduced pressure
  4. customto give a syrup
  5. temperaturecooled at 0°-5° C. under atmosphere of nitrogen
  6. stirringThe mixture was stirred at 0°-5° C. for one hour and at ambient temperature for 3 hours
  7. washThe organic layer was washed with water (60 ml) and brine (60 ml) in turn
  8. dry with materialdried over magnesium sulfate
  9. concentrationconcentrated under reduced pressure
  10. customto give a syrup
  11. washeluted with a mixture of hexane and ethyl acetate (4:1 V/V)

出典と根拠

ORDレコード
ord-7115ee5f57614283ba11b69498adc394
出典データセット
uspto-grants-1991_01
特許番号
US04983596

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