N-bromobutanimide → HCID 66620898、化合物

HRID 71900ノート

反応式

HRID 71900 の反応式
[Br:1][C:2]1[CH:15]=[CH:14][C:13]2[C:12]3[C:7](=[CH:8][C:9](Br)=[CH:10][CH:11]=3)[CH2:6][CH2:5][C:4]=2[CH:3]=1.C([Sn](CCCC)(CCCC)[C:22]([O:24]CC)=[CH2:23])CCC.C1C(=O)N(Br)C(=O)C1.[C:43]([O:47][C:48]([N:50]1[CH2:54][CH2:53][CH2:52][CH:51]1[C:55]([OH:57])=[O:56])=[O:49])([CH3:46])([CH3:45])[CH3:44].CCN(C(C)C)C(C)C>O1CCOCC1.C(OCC)(=O)C.C(#N)C.O>[C:43]([O:47][C:48]([N:50]1[CH2:54][CH2:53][CH2:52][CH:51]1[C:55]([O:57][CH2:23][C:22]([C:9]1[CH:10]=[CH:11][C:12]2[C:13]3[C:4](=[CH:3][C:2]([Br:1])=[CH:15][CH:14]=3)[CH2:5][CH2:6][C:7]=2[CH:8]=1)=[O:24])=[O:56])=[O:49])([CH3:46])([CH3:44])[CH3:45]

参加物

10

反応物 5

HCID 67184N-bromobutanimideHCID 81531DiisopropylethylamineHCID 2684721-[(Tert-butoxy)carbonyl]pyrrolidine-2-carboxylic acidHCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 28250532,7-Dibromo-9,10-dihydrophenanthrene

生成物 1

HCID 66620898HCID 66620898、化合物

試薬・触媒・溶媒 4

HCID 962Water溶媒HCID 6342Acetonitrile溶媒HCID 8857Ethyl Acetate溶媒2 回HCID 312751,4-Dioxane溶媒

反応条件

温度
80 °C

実験手順

Pd(Ph3)4 (347 mg, 0.3 mmol) and PdCl2(Ph3)2 (210 mg, 0.3 mmol) were added to a mixture 2,7-dibromo-9,10-dihydro-phenanthrene (2.5 g, 7.4 mmol) and tributyl(1-ethoxyvinyl)tin (2.5 mL, 7.4 mL) in 70 mL dioxane. The reaction mixture was flushed with nitrogen, heated at 80° C. for 16 hours, then cooled to ambient temperature. Water (20 mL) and NBS (1.39 g, 7.8 mmol) were added and the mixture was stirred at room temperature for 40 minutes, then diluted with ethyl acetate (300 mL). Washed with water and brine, dried over Na2SO4, filtered and concentrated in vacuo. The obtained residue was suspended in acetonitrile (70 mL). To it was added a solution of pyrrolidine-1,2-dicarboxylic acid 1-tert-butyl ester (3.2 g, 14.9 mmol) and DIPEA (2.4 mL, 14.1 mmol) in 20 mL acetonitrile. The mixture was stirred at room temperature for 16 hours, then diluted with ethyl acetate (300 mL). The organic layer was washed with NaHCO3 solution and water, dried over Na2SO4, filtered and concentrated in vacuo. The obtained residue was purified by flash chromatography to provide the desired product pyrrolidine-1,2-dicarboxylic acid 2-[2-(7-bromo-9,10-dihydro-phenanthren-2-yl)-2-oxo-ethyl]ester 1-tert-butyl ester as a white solid (1.76 g, 46% over two steps). m/z 514.2, 516.2 (M+H)+.

後処理

  1. customThe reaction mixture was flushed with nitrogen
  2. temperaturecooled to ambient temperature
  3. washWashed with water and brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. stirringThe mixture was stirred at room temperature for 16 hours
  8. washThe organic layer was washed with NaHCO3 solution and water
  9. dry with materialdried over Na2SO4
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo
  12. customThe obtained residue was purified by flash chromatography

出典と根拠

ORDレコード
ord-eb3f48f349a44a2b963f84f75820ca5f
出典データセット
uspto-grants-2014_09
特許番号
US08822430B2

反応ノート

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