Allyl bromide → (2S,4R)-1-tert-butyl 2-ethyl 4-allyl-5-oxopyrrolidine-1,2-dicarboxylate

HRID 218413ノート

反応式

HRID 218413 の反応式
C[Si](N[Si](C)(C)C)(C)C.[Li][CH2:11][CH2:12][CH2:13]C.[O:15]=[C:16]1[N:20]([C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])[C@H:19]([C:28]([O:30][CH2:31][CH3:32])=[O:29])[CH2:18][CH2:17]1.C[Si](C)(C)[N-][Si](C)(C)C.[Li+].BrCC=C>C1COCC1.CCCCCC>[CH2:13]([C@H:17]1[C:16](=[O:15])[N:20]([C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])[C@H:19]([C:28]([O:30][CH2:31][CH3:32])=[O:29])[CH2:18]1)[CH:12]=[CH2:11]

参加物

8

反応物 5

HCID 7841Allyl bromideHCID 13838HexamethyldisilazaneHCID 2733832Lithium HexamethyldisilazideHCID 54611861-(1,1-Dimethylethyl) 2-ethyl (2S)-5-oxo-1,2-pyrrolidinedicarboxylateHCID 178418339Butyllithium

生成物 1

HCID 5287387(2S,4R)-1-tert-butyl 2-ethyl 4-allyl-5-oxopyrrolidine-1,2-dicarboxylate収率 16%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒4 回HCID 8058Hexane溶媒

反応条件

温度
-78 °C

実験手順

To a solution of HMDS in anhydrous THF (200 mL) was added dropwise 2.5 M n-BuLi in hexane (130 mL) and the mixture was stirred at −78° C. for 1 hr. To a solution of (S)-1-tert-butyl 2-ethyl 5-oxopyrrolidine-1,2-dicarboxylate (80 g, 0.311 mol) in anhydrous THF (1600 mL) stirred at −78° C. was added lithium hexamethyldisilazide in THF. After the reaction mixture was stirred at −78° C. for 1 hr, 3-bromopropene (38.47 g, 0.318 mol) in THF (200 mL) was added and stirring was continued for 2 hr. The reaction mixture was quenched with saturated ammonium chloride solution (600 mL) at −78° C. and extracted with EtOAc (3×500 mL). The combined organic layers were dried over Na2SO4, filtered and evaporated to dryness. The crude product was separated by column chromatography to afford (2S,4R)-1-tert-butyl 2-ethyl 4-allyl-5-oxopyrrolidine-1,2-dicarboxylate (15 g, 16%).

後処理

  1. stirringAfter the reaction mixture was stirred at −78° C. for 1 hr
  2. stirringstirring
  3. waitwas continued for 2 hr
  4. customThe reaction mixture was quenched with saturated ammonium chloride solution (600 mL) at −78° C.
  5. extractionextracted with EtOAc (3×500 mL)
  6. dry with materialThe combined organic layers were dried over Na2SO4
  7. filtrationfiltered
  8. customevaporated to dryness
  9. customThe crude product was separated by column chromatography

出典と根拠

ORDレコード
ord-0488bea7743145bda9045f7f1e166a92
出典データセット
uspto-grants-2012_06
特許番号
US08198453B2

反応ノート

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