Diisopropylamine → (3S,4S)-3-[(1R)-1-(tert-butyldimethylsilyloxy)ethyl]-4-[(1R)-1-[(methylthio)thiocarbonyl}ethyl]-2-oxoazetidine

HRID 1464723

反応式

HRID 1464723 の反応式
C(NC(C)C)(C)C.C([Li])CCC.[C:13]([S:17][CH3:18])(=[S:16])[CH2:14][CH3:15].C(O[C@H:23]1[NH:26][C:25](=[O:27])[C@@H:24]1[C@H:28]([O:30][Si:31]([C:34]([CH3:37])([CH3:36])[CH3:35])([CH3:33])[CH3:32])[CH3:29])(=O)C>O1CCCC1.CCCCCC.CC(C)[O-].CC(C)[O-].CC(C)[O-].Cl[Ti+3]>[Si:31]([O:30][C@@H:28]([C@@H:24]1[C@@H:23]([C@H:14]([C:13]([S:17][CH3:18])=[S:16])[CH3:15])[NH:26][C:25]1=[O:27])[CH3:29])([C:34]([CH3:35])([CH3:36])[CH3:37])([CH3:32])[CH3:33]

参加物

8

反応物 4

HCID 7912DiisopropylamineHCID 223580Methyl propanedithioateHCID 10935078AzetidonHCID 178418339Butyllithium

生成物 1

HCID 57309161(3S,4S)-3-[(1R)-1-(tert-butyldimethylsilyloxy)ethyl]-4-[(1R)-1-[(methylthio)thiocarbonyl}ethyl]-2-oxoazetidine収率 58.2%

試薬・触媒・溶媒 3

HCID 11673339Chlorotitaniumtriisopropoxide触媒HCID 8028Tetrahydrofuran溶媒HCID 8058Hexane溶媒2 回

反応条件

温度
0 °C

実験手順

To a solution of diisopropylamine (152 mg) in anhydrous tetrahydrofuran (2 ml) cooled to 0° C. was added a 1.56M solution of n-butyllithium in n-hexane (0.95 ml). After stirring for 30 minutes at 0° C., the solution was cooled to -78° C. and methyl dithiopropionate (120 mg) and a 1M solution of chlorotitanium triisopropoxide in hexane (4.0 ml) were added successively thereto. The mixture was warmed to -40° C. and (3R,4R)-4-acetoxy-3-[(1R)-1-(tert-butyldimethylsilyloxy)ethyl]-2-oxoazetidine (287 mg) was added thereto. The solution was allowed to warm to 0° C., quenched by 1N hydrochrolic acid, and extracted with diethyl ether. The organic layer was washed with brine, dried, and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (10% diethyl ether-hexane) to afford a mixture (202 mg) of (3S,4S)-3-[(1R)-1-(tert-butyldimethylsilyloxy)ethyl]-4 -[(1R)-1-[(methylthio)thiocarbonyl}ethyl]-2-oxoazetidine and (3S,4S)-3-[(1R)-1-(tert-butyldimethylsilyloxy)ethyl]-4-[(1S)-1-{(methylthio)thiocarbonyl}ethyl]-2-oxoazetidine. Recrystallization of the product obtained above from n-hexane gave (3S,4S)-3-[(1R)-1-(tert-butyldimethylsilyloxy)ethyl]-4-[(1R)-1-{(methylthio)thiocarbonyl}ethyl]-2-oxoazetidine as a yellow needle.

後処理

  1. temperaturethe solution was cooled to -78° C.
  2. temperatureThe mixture was warmed to -40° C.
  3. temperatureto warm to 0° C.
  4. customquenched by 1N hydrochrolic acid
  5. extractionextracted with diethyl ether
  6. washThe organic layer was washed with brine
  7. customdried
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was purified by flash chromatography on silica gel (10% diethyl ether-hexane)

出典と根拠

ORDレコード
ord-88ffb50b26f04ca5bdb257093b834648
出典データセット
uspto-grants-1994_04
特許番号
US05306816

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