Butanal → tert-Butyl 8-butyryl-3,4-dihydropyrazino[1,2-a]indole-2(1H)-carboxylate

HRID 1481748ノート

反応式

HRID 1481748 の反応式
Br[C:2]1[CH:10]=[CH:9][C:8]2[N:7]3[CH2:11][CH2:12][N:13]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:14][C:6]3=[CH:5][C:4]=2[CH:3]=1.CN(C=O)C.N1CCCC1.[CH:32](=[O:36])[CH2:33][CH2:34][CH3:35]>CCOC(C)=O.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1>[C:32]([C:2]1[CH:10]=[CH:9][C:8]2[N:7]3[CH2:11][CH2:12][N:13]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:14][C:6]3=[CH:5][C:4]=2[CH:3]=1)(=[O:36])[CH2:33][CH2:34][CH3:35]

参加物

8

反応物 4

HCID 261ButanalHCID 6228DimethylformamideHCID 31268PyrrolidineHCID 712847451,1-Dimethylethyl 8-bromo-3,4-dihydropyrazino[1,2-a]indole-2(1H)-carboxylate

生成物 1

HCID 71284792tert-Butyl 8-butyryl-3,4-dihydropyrazino[1,2-a]indole-2(1H)-carboxylate収率 73%

試薬・触媒・溶媒 3

HCID 634876Binap, (A+-)-触媒HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladium触媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
115 °C

実験手順

To a vial was added tert-butyl 8-bromo-3,4-dihydropyrazino[1,2-a]indole-2(1H)-carboxylate (1.4 g, 4.0 mmol), Pd(dba)2 (75 mg, 2 mol %), BINAP (75 mg, 3 mol %), and crushed 4 Å MS (2.0 g). The vial was evacuated and backfilled under argon. To the vial was then added DMF (15 mL), pyrrolidine (660 μL, 8.0 mmol), and butyraldehyde (1.0 mL, 12 mmol). The vial was then sealed under argon and heated to 115° C. for 6 h. The reaction mixture was then cooled to room temperature, diluted with EtOAc (50 mL), and filtered through celite. The filtrate was washed with H2O (50 mL) and brine (50 mL). The organic layer was dried over Na2SO4, filtered, and concentrated to afford a crude residue that was purified on silica gel (1:1 hexanes/EtOAc) to afford the title compound as a white solid (1.0 g, 73%).

後処理

  1. customcrushed 4 Å MS (2.0 g)
  2. customThe vial was evacuated
  3. customThe vial was then sealed under argon
  4. temperatureThe reaction mixture was then cooled to room temperature
  5. filtrationfiltered through celite
  6. washThe filtrate was washed with H2O (50 mL) and brine (50 mL)
  7. dry with materialThe organic layer was dried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customto afford a crude residue that
  11. customwas purified on silica gel (1:1 hexanes/EtOAc)

出典と根拠

ORDレコード
ord-fe37c7dc42b44f2c9067944d3ddc7b26
出典データセット
uspto-grants-2016_08
特許番号
US09409905B2

反応ノート

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