Tetrahydrofuran → (3S,7aR)-6,6-Dibenzyl-3-tert-butyl-1,6,7,7a-tetrahydro-5-oxopyrrolo[1,2-c]oxazole-7a-carboxylic Acid Methyl Ester

HRID 1359174

反応式

HRID 1359174 の反応式
[CH3:1][O:2][C:3]([C@:5]12[CH2:16][CH2:15][C:14](=[O:17])[N:6]1[C@H:7]([C:10]([CH3:13])([CH3:12])[CH3:11])[O:8][CH2:9]2)=[O:4].[Li+].[CH3:19][CH:20]([N-]C(C)C)[CH3:21].CN(P(N(C)C)(N(C)C)=O)C.BrCCC[CH:41]([C:48]1[CH:53]=[CH:52][CH:51]=[CH:50][CH:49]=1)C1C=CC=CC=1.[CH2:54]1[CH2:58]O[CH2:56][CH2:55]1>>[CH3:1][O:2][C:3]([C@:5]12[CH2:16][C:15]([CH2:41][C:48]3[CH:49]=[CH:50][CH:51]=[CH:52][CH:53]=3)([CH2:56][C:55]3[CH:21]=[CH:20][CH:19]=[CH:58][CH:54]=3)[C:14](=[O:17])[N:6]1[C@H:7]([C:10]([CH3:13])([CH3:12])[CH3:11])[O:8][CH2:9]2)=[O:4]

参加物

6

反応物 5

HCID 8028Tetrahydrofuran2 回HCID 12679HexamethylphosphoramideHCID 2724682Lithium diisopropylamideHCID 11053798(3S,7aR)-3-tert-Butyl-1,6,7,7a-tetrahydro-5-oxopyrrolo[1,2-c]oxazole-7a-carboxylic Acid Methyl Ester2 回HCID 122234581,1-Diphenyl-4-bromobutane

生成物 1

HCID 11069859(3S,7aR)-6,6-Dibenzyl-3-tert-butyl-1,6,7,7a-tetrahydro-5-oxopyrrolo[1,2-c]oxazole-7a-carboxylic Acid Methyl Ester

実験手順

To a solution of bicycle 17 (260 mg, 1.08 mmol) in THF (7.0 mL) under nitrogen were added at −78° C. successively a solution of LDA (1.5 M, 1.0 mL) and HMPA (1.0 mL). After 1 h, 4-bromo-1,1-diphenylbutane (360 mg, 1.25 mmol) in THF (3.0 mL) was added. After 6 h at −78° C., the reaction mixture was quenched with saturated NH4Cl solution. The product was extracted into EtOAc, and the combined organic layers were washed with brine, dried (Na2SO4), and concentrated under reduced pressure. Separation by column chromatography (SiO2, hexane/EtOAc 30:1) afforded starting material 17 (140 mg, 54% recovery) and compound 14g (70 mg, 31%) besides traces of 14h (2 mg) and 14i (2 mg).

後処理

  1. waitAfter 6 h at −78° C.
  2. customthe reaction mixture was quenched with saturated NH4Cl solution
  3. extractionThe product was extracted into EtOAc
  4. washthe combined organic layers were washed with brine
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated under reduced pressure
  7. customSeparation by column chromatography (SiO2, hexane/EtOAc 30:1)
  8. customafforded

出典と根拠

ORDレコード
ord-d2c3645142db4131a886605b00405aeb
出典データセット
uspto-grants-2003_07
特許番号
US06599940B2

関連ノート

読み込み中…