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Diisopropylamine → 2-(4-Bromo-2-fluoro-benzyl)-3-tert-butoxycarbonylamino-propionic acid tert-butyl ester

HRID 1192375
ノート
印刷プレビュー

反応式

HRID 1192375 の反応式
C(NC(C)C)(C)C.[Li]CCCC.[C:13]([O:17][C:18](=[O:29])[CH2:19][CH2:20][NH:21][C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])([CH3:16])([CH3:15])[CH3:14].[Br:30][C:31]1[CH:36]=[CH:35][C:34]([CH2:37]Br)=[C:33]([F:39])[CH:32]=1>C1COCC1>[C:13]([O:17][C:18](=[O:29])[CH:19]([CH2:37][C:34]1[CH:35]=[CH:36][C:31]([Br:30])=[CH:32][C:33]=1[F:39])[CH2:20][NH:21][C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])([CH3:16])([CH3:15])[CH3:14]
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

6

反応物 4

HCID 7912DiisopropylamineHCID 27336604-Bromo-2-fluorobenzyl bromideHCID 540966173-Tert-butoxycarbonylamino-propionic acid tert-butyl esterHCID 178418339Butyllithium

生成物 1

HCID 675390002-(4-Bromo-2-fluoro-benzyl)-3-tert-butoxycarbonylamino-propionic acid tert-butyl ester収率 77%

試薬・触媒・溶媒 1

HCID 8028
Tetrahydrofuran
溶媒
3 回

反応条件

温度
0 °C

実験手順

To a stirred solution of diisopropyl amine (1.3 mL, 9.0 mmol) in THF (20 mL) was added n-BuLi (1.6 M solution in hexanes, 5.6 mL, 9.0 mmol) at 0° C. The reaction was stirred at 0° C. for 15 minutes and then cooled to −78° C. A solution of 3-tert-butoxycarbonylamino-propionic acid tert-butyl ester (1.0 g, 4.1 mmol) in THF (5 mL) was added dropwise. The mixture was stirred at −78° C. for 2 hours. A solution of 4-Bromo-1-bromomethyl-2-fluoro-benzene (1.3 g, 4.9 mmol) in THF (4 mL) was added dropwise. After completion, the dry-ice bath was removed and the reaction was warmed to 0° C. in an ice bath. After stirring at 0° C. for 30 minutes, the reaction was poured into saturated NH4Cl aqueous solution. The organic layer was separated. The aqueous layer was extracted with EtOAc. The combined organic layers were washed with brine, dried and concentrated. The residue was purified by column chromatography (hexane:EtOAc, 20:1 to 5:1) to give 2-(4-Bromo-2-fluoro-benzyl)-3-tert-butoxycarbonylamino-propionic acid tert-butyl ester (1.35 g, 77%) as a colorless oil. 1H NMR (CDCl3, 400 MHz) δ 7.20 (d, J=8.0 Hz, 2H), 7.08 (t, J=8.0 Hz, 1H), 4.86 (m, 1H), 3.28 (m, 2H), 2.92 (m, 3H), 1.43 (s, 9H), 1.36 (s, 9H).

後処理

  1. temperaturecooled to −78° C
  2. stirringThe mixture was stirred at −78° C. for 2 hours
  3. customAfter completion, the dry-ice bath was removed
  4. temperaturethe reaction was warmed to 0° C. in an ice bath
  5. stirringAfter stirring at 0° C. for 30 minutes
  6. additionthe reaction was poured into saturated NH4Cl aqueous solution
  7. customThe organic layer was separated
  8. extractionThe aqueous layer was extracted with EtOAc
  9. washThe combined organic layers were washed with brine
  10. customdried
  11. concentrationconcentrated
  12. customThe residue was purified by column chromatography (hexane:EtOAc, 20:1 to 5:1)

出典と根拠

ORDレコード
ord-87df00e4904c40e3b84c626a82ae0c56
出典データセット
uspto-grants-2014_03
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08680114B2

反応ノート

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