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tert-Butyl acrylate → (E)-Benzyl 4-(4-(3-tert-butoxy-3-oxoprop-1-enyl)-3-(dibutylcarbamoyl)-5-methyl-1H-pyrazol-1-yl)-3-(1,2,3,4-tetrahydroisoquinoline-2-carbonyl)benzoate

HRID 528924
ノート
印刷プレビュー

反応式

HRID 528924 の反応式
Br[C:2]1[C:3]([C:36](=[O:46])[N:37]([CH2:42][CH2:43][CH2:44][CH3:45])[CH2:38][CH2:39][CH2:40][CH3:41])=[N:4][N:5]([C:8]2[CH:23]=[CH:22][C:11]([C:12]([O:14][CH2:15][C:16]3[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=3)=[O:13])=[CH:10][C:9]=2[C:24]([N:26]2[CH2:35][CH2:34][C:33]3[C:28](=[CH:29][CH:30]=[CH:31][CH:32]=3)[CH2:27]2)=[O:25])[C:6]=1[CH3:7].[C:47]([O:51][C:52]([CH3:55])([CH3:54])[CH3:53])(=[O:50])[CH:48]=[CH2:49]>CN(C=O)C.CCN(CC)CC.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[C:52]([O:51][C:47](=[O:50])/[CH:48]=[CH:49]/[C:2]1[C:3]([C:36](=[O:46])[N:37]([CH2:38][CH2:39][CH2:40][CH3:41])[CH2:42][CH2:43][CH2:44][CH3:45])=[N:4][N:5]([C:8]2[CH:23]=[CH:22][C:11]([C:12]([O:14][CH2:15][C:16]3[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=3)=[O:13])=[CH:10][C:9]=2[C:24]([N:26]2[CH2:35][CH2:34][C:33]3[C:28](=[CH:29][CH:30]=[CH:31][CH:32]=3)[CH2:27]2)=[O:25])[C:6]=1[CH3:7])([CH3:55])([CH3:54])[CH3:53]
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 2

HCID 15458tert-Butyl acrylateHCID 71062156Benzyl 4-(4-bromo-3-(dibutylcarbamoyl)-5-methyl-1H-pyrazol-1-yl)-3-(1,2,3,4-tetrahydroisoquinoline-2-carbonyl)benzoate2 回

生成物 1

HCID 71062592(E)-Benzyl 4-(4-(3-tert-butoxy-3-oxoprop-1-enyl)-3-(dibutylcarbamoyl)-5-methyl-1H-pyrazol-1-yl)-3-(1,2,3,4-tetrahydroisoquinoline-2-carbonyl)benzoate収率 50%

試薬・触媒・溶媒 3

HCID 178418476
HCID 178418476、化合物
触媒
HCID 6228Dimethylformamide溶媒
HCID 8471Triethylamine溶媒

反応条件

温度
140 °C

実験手順

To a solution of benzyl 4-(4-bromo-3-(dibutylcarbamoyl)-5-methyl-1H-pyrazol-1-yl)-3-(1,2,3,4-tetrahydroisoquinoline-2-carbonyl)benzoate (Intermediate 164A, 80 mg, 0.12 mmol) in DMF (580 μL) and Et3N (580 μL) was added (PPh3)2PdCl2 (8 mg, 0.012 mmol) followed by tert-butyl acrylate (58 μL, 0.40 mmol). The reaction mixture was purged with N2 for 5 min and then heated at 140° C. overnight. The reaction mixture was poured into a separatory funnel containing 1N aq. HCl solution and EtOAc. The organic layer was washed 1N aq. HCl solution (2×) and the aqueous layer was extracted with EtOAc (3×). The combined organic extracts were washed with sat. aq. NaHCO3 solution, dried over Na2SO4 and concentrated in vacuo. The residue was purified by flash chromatography (gradient from 0% to 35% EtOAc/hexanes) to provide the title compound (42 mg, 50%) as a colorless oil. MS(ESI+) m/z 733.5 (M+H)+.

後処理

  1. customThe reaction mixture was purged with N2 for 5 min
  2. additionThe reaction mixture was poured into a separatory funnel
  3. additioncontaining 1N aq. HCl solution and EtOAc
  4. washThe organic layer was washed 1N aq. HCl solution (2×)
  5. extractionthe aqueous layer was extracted with EtOAc (3×)
  6. washThe combined organic extracts were washed with sat. aq. NaHCO3 solution
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified by flash chromatography (gradient from 0% to 35% EtOAc/hexanes)

出典と根拠

ORDレコード
ord-8a7293510f9c4e6c91071d013ed97a7b
出典データセット
uspto-grants-2016_05
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US09346795B2

反応ノート

読み込み中…

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