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

HRID 1464723

반응식

HRID 1464723 반응식
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]

참가 물질

8

반응물 4

HCID 7912DiisopropylamineHCID 223580Methyl propanedithioateHCID 10935078AzetidonHCID 178418339Butyllithium

생성물 1

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

시약·촉매·용매 3

HCID 11673339Chlorotitaniumtriisopropoxide촉매HCID 8028Tetrahydrofuran용매HCID 8058Hexane용매2회

반응 조건

온도
0 °C

실험 절차

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.

후처리

  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)

출처 및 근거

ORD 기록
ord-88ffb50b26f04ca5bdb257093b834648
출처 데이터셋
uspto-grants-1994_04
특허 번호
US05306816

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