Cesium carbonate → 5-Ethenyl-1H-indole

HRID 1502982ノート

反応式

HRID 1502982 の反応式
Br[C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[NH:7][CH:6]=[CH:5]2.[CH:11]([B-](F)(F)F)=[CH2:12].[K+].C([O-])([O-])=O.[Cs+].[Cs+].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1COCC1.O.Cl[Pd]Cl>[CH:11]([C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[NH:7][CH:6]=[CH:5]2)=[CH2:12]

参加物

7

反応物 4

HCID 10796Cesium carbonateHCID 11776TriphenylphosphineHCID 249055-BromoindoleHCID 23679353Potassium vinyltrifluoroborate

生成物 1

HCID 126103725-Ethenyl-1H-indole

試薬・触媒・溶媒 2

HCID 24290Palladium Chloride触媒HCID 21881883Oxolane--water (1/1)溶媒

実験手順

A mixture of 5-bromo-1H-indole (2.5 g, 12.82 mmol), potassium vinyltrifluoroborate (2.57 g, 19.2 mmol), Cs2CO3 (12.53 g, 38.46 mmol) and triphenylphosphine (201 mg, 0.769 mmol) in THF/water (9:1, 75 ml) was degassed with argon for 20 min, then charged with PdCl2 (45.3 mg, 0.256 mmol). The reaction mixture was heated to reflux for 16 h, then cooled to ambient temperature, filtered through celite bed and washed with ethyl acetate. The filtrate was again extracted with ethyl acetate, and the combined organic layer washed with water and brine, dried over Na2SO4 and concentrated under reduced pressure to afford the crude compound. The crude compound was purified by column chromatography (SiO2, 100-200 mesh; 2% ethyl acetate/petroleum ether) to afford the title compound as a light brown gummy material (1.5 g, 83%): 1H NMR (400 MHz, CDCl3) δ 8.20 (br, 1H), 7.68 (s, 1H), 7.45 (s, 2H), 7.21 (m, 1H), 6.90 (dd, J=16.0, 10.8 Hz, 1H), 6.55 (m, 1H), 5.75 (d, J=10.5 Hz, 1H), 5.21 (d, J=10.5 Hz, 1H); ESIMS m/z 142.05 ([M−H−]).

後処理

  1. customwas degassed with argon for 20 min
  2. temperatureThe reaction mixture was heated
  3. temperatureto reflux for 16 h
  4. filtrationfiltered through celite bed
  5. washwashed with ethyl acetate
  6. extractionThe filtrate was again extracted with ethyl acetate
  7. washthe combined organic layer washed with water and brine
  8. dry with materialdried over Na2SO4
  9. concentrationconcentrated under reduced pressure
  10. customto afford the crude compound
  11. customThe crude compound was purified by column chromatography (SiO2, 100-200 mesh; 2% ethyl acetate/petroleum ether)

出典と根拠

ORDレコード
ord-c3fe33a8b8124dcabfafbf1225e86d17
出典データセット
uspto-grants-2015_12
特許番号
US09211281B2

反応ノート

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