Acetone → Methyl (1R,4S)-4-[(tert-butoxycarbonyl)amino]-1-(1-hydroxy-1-methylethyl)cyclopent-2-ene-1-carboxylate

HRID 270592

反応式

HRID 270592 の反応式
C[Si](C)(C)[N-][Si](C)(C)C.[Li+].[C:11]([O:15][C:16]([NH:18][C@H:19]1[CH2:23][C@@H:22]([C:24]([O:26][CH3:27])=[O:25])[CH:21]=[CH:20]1)=[O:17])([CH3:14])([CH3:13])[CH3:12].C(Cl)(Cl)(Cl)Cl.C(=O)=O.[CH3:36][C:37]([CH3:39])=[O:38]>O1CCCC1>[C:11]([O:15][C:16]([NH:18][C@H:19]1[CH2:23][C@@:22]([C:37]([OH:38])([CH3:39])[CH3:36])([C:24]([O:26][CH3:27])=[O:25])[CH:21]=[CH:20]1)=[O:17])([CH3:14])([CH3:13])[CH3:12]

参加物

6

反応物 4

HCID 180AcetoneHCID 2733832Lithium HexamethyldisilazideHCID 10610130(1R,4S)-methyl 4-(tert-butoxycarbonylamino)cyclopent-2-enecarboxylateHCID 86602444Carbontetrachloride dry-ice

生成物 1

HCID 59833557Methyl (1R,4S)-4-[(tert-butoxycarbonyl)amino]-1-(1-hydroxy-1-methylethyl)cyclopent-2-ene-1-carboxylate収率 22.6%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
-78 °C

実験手順

To a 1.00 M solution of lithium hexamethyldisilazide in tetrahydrofuran (45 mL) stirring at −78° C. was added a solution of methyl (1R,4S)-4-[(tert-butoxycarbonyl)amino]cyclopent-2-ene-1-carboxylate (5.0 g, 21 mmol) in tetrahydrofuran (40 mL). The resulting golden mixture was warmed to −28° C. to −23° C. (CCl4/dry ice) and stirred for 30 min. The reaction solution was cooled down to −78° C. and anhydrous acetone (1.8 mL, 25 mmol) was added. After the addition, the reaction mixture was kept in a CCl4/dry ice bath and allowed to warm to room temperature overnight. The dark solution was quenched with saturated NH4Cl and extracted with ether three times. The combined extracts were dried, filtered, concentrated. The crude residue was purified by flash column chromatography (EtOAc/Hexane) to yield the desired product (1.4 g, 22.6%).

後処理

  1. additionAfter the addition
  2. customthe reaction mixture was kept in a CCl4/dry ice bath
  3. temperatureto warm to room temperature overnight
  4. customThe dark solution was quenched with saturated NH4Cl
  5. extractionextracted with ether three times
  6. customThe combined extracts were dried
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe crude residue was purified by flash column chromatography (EtOAc/Hexane)

出典と根拠

ORDレコード
ord-eafb2cef906f424dbdc33dc6cfdfca03
出典データセット
uspto-grants-2008_11
特許番号
US07449467B2

関連ノート

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