Diisopropylethylamine → HCID 57102959、化合物

HRID 703596

反応式

HRID 703596 の反応式
[N+](=[C:3]([C:10](=O)[C@@H:11]([C@@H:13]1[C@@H:16]([C@H:17]([O:19][Si:20]([C:23]([CH3:26])([CH3:25])[CH3:24])([CH3:22])[CH3:21])[CH3:18])[C:15](=[O:27])[NH:14]1)[CH3:12])[C:4]([O:6][CH2:7][CH:8]=[CH2:9])=[O:5])=[N-].C(N(C(C)C)CC)(C)C.C([S:41][C@@H:42]1[CH2:46][N:45]([C:47]([O:49][CH2:50][CH:51]=[CH2:52])=[O:48])[C@H:44]([CH2:53][O:54][CH2:55][CH2:56][OH:57])[CH2:43]1)(=O)C.C[O-].[Na+]>C(OCC)(=O)C.C(#N)C.CO.C([O-])(=O)CCCCCCC.[Rh+2].C([O-])(=O)CCCCCCC>[CH2:50]([O:49][C:47]([N:45]1[CH2:46][C@@H:42]([S:41][C:10]2[C@H:11]([CH3:12])[C@H:13]3[N:14]([C:15](=[O:27])[C@@H:16]3[C@H:17]([O:19][Si:20]([C:23]([CH3:26])([CH3:24])[CH3:25])([CH3:22])[CH3:21])[CH3:18])[C:3]=2[C:4]([O:6][CH2:7][CH:8]=[CH2:9])=[O:5])[CH2:43][C@H:44]1[CH2:53][O:54][CH2:55][CH2:56][OH:57])=[O:48])[CH:51]=[CH2:52]

参加物

9

反応物 4

HCID 81531DiisopropylethylamineHCID 10942334Sodium MethoxideHCID 18642553HCID 18642553、化合物HCID 131715918HCID 131715918、化合物

生成物 1

HCID 57102959HCID 57102959、化合物収率 42.7%

試薬・触媒・溶媒 4

HCID 10178397Rhodium(II) octanoate触媒2 回HCID 887Methanol溶媒HCID 6342Acetonitrile溶媒2 回HCID 8857Ethyl Acetate溶媒2 回

実験手順

To a solution of allyl (4R)-2-diazo-4-[(2R,3S)-3-{(1R)-1-(t-butyldimethylsilyloxy)ethyl}-4-oxoazetidine-2-yl]-3-oxopentanoate (13.5 g) in ethyl acetate (65 ml) was added rhodium(II) octanoate (50 mg) under refluxing in a stream of nitrogen. After 20 minutes, rhodium(II) octanoate (50 mg) was added to the mixture at the same condition. The mixture was refluxed for 30 minutes and concentrated under reduced pressure to give a syrup. The syrup was dissolved in acetonitrile (65 ml) and cooled at 0°-5° C. under atmosphere of nitrogen. To the solution was added diphenyl phosphorochloride (7.52 ml) and N,N-diisopropyl-N-ethylamine (6.31 ml) successively and the mixture was stirred at the same condition for 18 hours (solution A). To a solution of (2S,4S)-4-acetylthio-1-allyloxycarbonyl-2-(2-hydroxyethyloxymethyl)pyrrolidine (10.7 g) in acetonitrile (40.5 ml) was added a 28% solution (6.92 ml) of sodium methoxide in methanol at -10°~0° C. in a stream of nitrogen and the mixture was stirred at the same condition (solution B). To the solution A was added the solution B at -10°~0° C. in a stream of nitrogen and the mixture was stirred at -10~0° C. for one hour and then at 10°-20° C. for 3 hours. Ethyl acetate (200 ml) was added to the mixture and the mixture was washed with water (200 ml×3), dried over magnesium sulfate, and concentrated under reduced pressure to give a syrup. The syrup was subjected to a column chromatography on silica gel (300 g) and eluted with ethyl acetate to give allyl (4R,5S,6S)-3-[(2S,4S)-1-allyloxycarbonyl-2-(2-hydroxyethyloxymethyl)pyrrolidin-4-yl]thio-6-[(1R)-1-(t-butyldimethylsilyloxy)ethyl]-4-methyl- 7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate (8.80 g).

後処理

  1. temperatureunder refluxing in a stream of nitrogen
  2. temperatureThe mixture was refluxed for 30 minutes
  3. concentrationconcentrated under reduced pressure
  4. customto give a syrup
  5. temperaturecooled at 0°-5° C. under atmosphere of nitrogen
  6. waitat 10°-20° C. for 3 hours
  7. washthe mixture was washed with water (200 ml×3)
  8. dry with materialdried over magnesium sulfate
  9. concentrationconcentrated under reduced pressure
  10. customto give a syrup
  11. washeluted with ethyl acetate

出典と根拠

ORDレコード
ord-0ecb44f20e014470963b8f251e8b3acd
出典データセット
uspto-grants-1991_01
特許番号
US04983596

関連ノート

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