methyl 7-(2-bromo-4-fluorobenzenesulfonylamino]-2,3-dihydro-1H-pyrrolo[1,2-a]indole-8-carboxylate → methyl 7-[2-((Z)-3-diethylaminoprop-1-enyl)-4-fluorobenzenesulfonylamino]-2,3-dihydro-1H-pyrrolo[1,2-a]indole-8-carboxylate

HRID 715953ノート

反応式

HRID 715953 の反応式
Br[C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[S:9]([NH:12][C:13]1[CH:21]=[CH:20][C:19]2[N:18]3[CH2:22][CH2:23][CH2:24][C:17]3=[CH:16][C:15]=2[C:14]=1[C:25]([O:27][CH3:28])=[O:26])(=[O:11])=[O:10].[CH2:29]([N:31]([CH2:48][CH3:49])[CH2:32]/[CH:33]=[CH:34]\[Sn](CCCC)(CCCC)CCCC)[CH3:30]>O1CCOCC1.CS(C)=O>[CH2:29]([N:31]([CH2:48][CH3:49])[CH2:32]/[CH:33]=[CH:34]\[C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[S:9]([NH:12][C:13]1[CH:21]=[CH:20][C:19]2[N:18]3[CH2:22][CH2:23][CH2:24][C:17]3=[CH:16][C:15]=2[C:14]=1[C:25]([O:27][CH3:28])=[O:26])(=[O:11])=[O:10])[CH3:30]

参加物

5

反応物 2

HCID 70984190methyl 7-(2-bromo-4-fluorobenzenesulfonylamino]-2,3-dihydro-1H-pyrrolo[1,2-a]indole-8-carboxylate2 回HCID 86684726N,N-diethyl-N-((Z)-1-tributylstannanylprop-1-en-3-yl)amine2 回

生成物 1

HCID 86712101methyl 7-[2-((Z)-3-diethylaminoprop-1-enyl)-4-fluorobenzenesulfonylamino]-2,3-dihydro-1H-pyrrolo[1,2-a]indole-8-carboxylate収率 90.7%

試薬・触媒・溶媒 2

HCID 679Dimethyl Sulfoxide溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
95 °C

実験手順

A mixture of methyl 7-(2-bromo-4-fluorobenzenesulfonylamino]-2,3-dihydro-1H-pyrrolo[1,2-a]indole-8-carboxylate (Intermediate 17, 0.100 g) and N,N-diethyl-N—((Z)- 1-tributylstannanylprop-1-en-3-yl)-amine (Intermediate 3, 0.172 g) in dioxane (2 mL) and DMSO (0.2 mL) was de-gassed and purged with nitrogen. Tris-(dibenzylideneacetone)-dipalladium (0.009 g) and tri-tert-butylphosphonium tetrafluoroborate (0.006 g) were added and the reaction mixture was heated at 95° C., under an atmosphere of nitrogen for 45 minutes. After cooling, the mixture was partitioned between ethyl acetate and water. The layers were separated and the aqueous layer was extracted with ethyl acetate. The combined organic layers were dried (MgSO4), filtered and the filtrate was concentrated in vacuo. The residue was purified by chromatography on silica, eluting with a mixture of methanol and DCM with a gradient of 0-7.5% to give methyl 7-[2-((Z)-3-diethylaminoprop-1-enyl)-4-fluorobenzenesulfonylamino]-2,3-dihydro-1H-pyrrolo[1,2-a]indole-8-carboxylate (0.097 g) as a yellow oil.

後処理

  1. customwas de-gassed
  2. custompurged with nitrogen
  3. additionTris-(dibenzylideneacetone)-dipalladium (0.009 g) and tri-tert-butylphosphonium tetrafluoroborate (0.006 g) were added
  4. temperatureAfter cooling
  5. customthe mixture was partitioned between ethyl acetate and water
  6. customThe layers were separated
  7. extractionthe aqueous layer was extracted with ethyl acetate
  8. dry with materialThe combined organic layers were dried (MgSO4)
  9. filtrationfiltered
  10. concentrationthe filtrate was concentrated in vacuo
  11. customThe residue was purified by chromatography on silica
  12. washeluting with a mixture of methanol and DCM with a gradient of 0-7.5%

出典と根拠

ORDレコード
ord-367d0332ee7f46a7a29008324d16f3e5
出典データセット
uspto-grants-2015_11
特許番号
US09187494B2

反応ノート

読み込み中…