Acetaldehyde → (3S,4R)-1-(t-butyldimethylsilyl)3-[(R)-1-hydroxyethyl]-4-[2,2,2-tri(methylthio)ethyl]azetidin-2-one

HRID 648682노트

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HRID 648682 반응식
C([Li])CCC.C(NC(C)C)(C)C.[Si:13]([N:20]1[C@H:23]([CH2:24][C:25]([S:30][CH3:31])([S:28][CH3:29])[S:26][CH3:27])[CH2:22][C:21]1=[O:32])([C:16]([CH3:19])([CH3:18])[CH3:17])([CH3:15])[CH3:14].[CH:33](=[O:35])[CH3:34]>O1CCCC1>[Si:13]([N:20]1[C@H:23]([CH2:24][C:25]([S:28][CH3:29])([S:26][CH3:27])[S:30][CH3:31])[C@@H:22]([C@H:33]([OH:35])[CH3:34])[C:21]1=[O:32])([C:16]([CH3:17])([CH3:19])[CH3:18])([CH3:15])[CH3:14]

참가 물질

6

반응물 4

HCID 177AcetaldehydeHCID 7912DiisopropylamineHCID 13003464(4S)-1-(t-butyldimethylsilyl)-4-(2,2,2-tri(methylthio)ethyl)azetidin-2-oneHCID 178418339Butyllithium

생성물 1

HCID 13104625(3S,4R)-1-(t-butyldimethylsilyl)3-[(R)-1-hydroxyethyl]-4-[2,2,2-tri(methylthio)ethyl]azetidin-2-one수율 50.4%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

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온도
-78 °C

실험 절차

n-Butyllithium (14.8 ml of 2.5N hexane solution, 37.0 mmol) is added by syringe to a solution of diisopropylamine (3.74 g, 37.0 mmol) in 180 ml of freshly distilled tetrahydrofuran at -78° C. The resulting solution is stirred at -78° C. for 15 min prior to the addition of a solution of (4S)-1-(t-butyldimethylsilyl)-4-[2,2,2-tri(methylthio)ethyl]azetidin-2-one (12.34 g, 35.16 mmol) in 35 ml of tetrahydrofuran. This solution is stirred at -78° C. for 10 min prior to the addition of acetaldehyde (4.62 g, 105 mmol). The solution is stirred for an additional 5 min. at -78° C. and then quenched by addition of saturated aqueous ammonium chloride solution, and allowed to warm to room temperature. The mixture is poured into 250 ml of ether and washed with water (2×100 ml) and brine and dried over magnesium sulfate. Removal of solutions in vacuo gives an oil which is chromatographed on a silica gel column (1:1 ether:petroleum ether) to give (3S, 4R)-1-(t-butyldimethylsilyl)-3-[(R)-1-hydroxyethyl]-4-[2,2,2-tri(methylthio)ethyl]azetidin-2-one (7.0 g, 50.4%) at Rf =0.2. The product can be recrystallized from petroleum ether. Alternatively, the trans R product can be isolated from the crude reaction mixture by direct crystallization from a petroleum ether solution.

후처리

  1. stirringThis solution is stirred at -78° C. for 10 min
  2. stirringThe solution is stirred for an additional 5 min. at -78° C.
  3. customquenched by addition of saturated aqueous ammonium chloride solution
  4. temperatureto warm to room temperature
  5. additionThe mixture is poured into 250 ml of ether
  6. washwashed with water (2×100 ml) and brine
  7. dry with materialdried over magnesium sulfate
  8. customRemoval of solutions in vacuo
  9. customgives an oil which
  10. customis chromatographed on a silica gel column (1:1 ether:petroleum ether)

출처 및 근거

ORD 기록
ord-4438622ce1e649c8804907eb8b5408f0
출처 데이터셋
uspto-grants-1988_04
특허 번호
US04736025

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