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Acetic Acid → 6-[(E)-3-tert-Butyldimethylsilyloxy-3-cyclohexylprop-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octane-2-one

HRID 462787
ノート
印刷プレビュー

反応式

HRID 462787 の反応式
[Si:1]([O:8][CH:9]([CH:21]1[CH2:26][CH2:25][CH2:24][CH2:23][CH2:22]1)/[CH:10]=[CH:11]/[CH:12]1[CH2:19][CH2:18][CH:17]2[CH:13]1[CH2:14][CH2:15][C:16]2=[O:20])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].C([N-]C(C)C)(C)C.[Li+].[CH3:35][O:36][C:37]([CH2:39][CH2:40][CH2:41][CH:42]=O)=[O:38].C(O)(=O)C>C(OCC)C.O>[Si:1]([O:8][CH:9]([CH:21]1[CH2:26][CH2:25][CH2:24][CH2:23][CH2:22]1)/[CH:10]=[CH:11]/[CH:12]1[CH2:19][CH2:18][CH:17]2[CH:13]1[CH2:14]/[C:15](=[CH:42]\[CH2:41][CH2:40][CH2:39][C:37]([O:36][CH3:35])=[O:38])/[C:16]2=[O:20])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

7

反応物 4

HCID 176Acetic AcidHCID 554053Pentanoic acid, 5-oxo-, methyl esterHCID 2724682Lithium diisopropylamideHCID 13241020(E)-2-(3-tert-Butyldimethylsilyloxy-3-cyclohexylprop-1-enyl)bicyclo[3,3,0]octan-6-one

生成物 1

HCID 203972036-[(E)-3-tert-Butyldimethylsilyloxy-3-cyclohexylprop-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octane-2-one収率 16.2%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 3283Diethyl Ether溶媒4 回

反応条件

温度
-70 °C

実験手順

(E)-2-(3-tert-Butyldimethylsilyloxy-3-cyclohexylprop-1-enyl)bicyclo[3,3,0]octan-6-one (57 mg), prepared as described in Reference Example 14 and in the form of (±)-(E)-2β-(3α-tert-butyldimethylsilyloxy-3-cyclohexylprop-1-enyl)bicyclo[3,3,0]octan-6-one, was dissolved in dry diethyl ether (0.6 ml). The solution was cooled to -70° C. under an atmosphere of argon and treated with a solution of lithium diisopropylamide in diethyl ether (0.132 ml; 1.3M) with stirring, and the mixture was stirred at -70° C. for 10 minutes. 4-Methoxycarbonylbutanal (29.6 mg) was then added to the mixture, which was stirred for a further period of 10 minutes at -70° C. The mixture was then treated with a solution of glacial acetic acid (0.05 ml) in diethyl ether (1 ml) and the mixture was allowed to warm to ambient temperature. Water and diethyl ether were added and the layers were separated. The aqueous layer was extracted with ethyl acetate. The combined diethyl ether and ethyl acetate solutions were washed with saturated aqueous sodium bicarbonate solution and then with saturated aqueous sodium chloride solution, dried over anhydrous sodium sulphate, and concentrated under reduced pressure. The resulting residue was dissolved in dry benzene (0.6 ml). The solution was treated with methanesulphonyl chloride (0.015 ml) with stirring at the ambient temperature, and then with triethylamine (0.0255 ml), and was stirred for a further period of 2 hours. The mixture was then treated with 1,8-diazabicyclo[5,4,0]undec-7-ene (137 mg) and stirred for 16 hours at ambient temperature. The crude mixture was then subjected to medium pressure, short column chromatography on silica gel, eluting with a mixture of ethyl acetate and hexane (1:9 by volume), to give (E)-6-(3-tert-butyldimethylsilyloxy-3-cyclohexylprop-1-enyl)-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one (12 mg), in the form of (±)-6β-[(E)-3α-tert-butyldimethylsilyloxy-3-cyclohexylprop-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one, otherwise known as (±)-methyl (5E,13E)-(9S,15S)-6a-oxo-6,9-methano-15-tert-butyldimethylsilyloxy-15-cyclohexyl-16,17,18,19,20-pentanorprosta-5,13-dienoate.

後処理

  1. stirringthe mixture was stirred at -70° C. for 10 minutes
  2. stirringwas stirred for a further period of 10 minutes at -70° C
  3. temperatureto warm to ambient temperature
  4. customthe layers were separated
  5. extractionThe aqueous layer was extracted with ethyl acetate
  6. washThe combined diethyl ether and ethyl acetate solutions were washed with saturated aqueous sodium bicarbonate solution
  7. dry with materialwith saturated aqueous sodium chloride solution, dried over anhydrous sodium sulphate
  8. concentrationconcentrated under reduced pressure
  9. dissolutionThe resulting residue was dissolved in dry benzene (0.6 ml)
  10. additionThe solution was treated with methanesulphonyl chloride (0.015 ml)
  11. stirringwith stirring at the ambient temperature
  12. stirringwith triethylamine (0.0255 ml), and was stirred for a further period of 2 hours
  13. additionThe mixture was then treated with 1,8-diazabicyclo[5,4,0]undec-7-ene (137 mg)
  14. stirringstirred for 16 hours at ambient temperature
  15. washeluting with a mixture of ethyl acetate and hexane (1:9 by volume)

出典と根拠

ORDレコード
ord-d580ec9804904a2f89d6e8af33fe6798
出典データセット
uspto-grants-1985_05
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US04517202

反応ノート

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