Tetrahydrofuran → (Z)-1-(2-(acetoxymethyl)-4-(tert-butoxycarbonylamino)-3-methylphenyl)-3-methoxy-3-oxoprop-1-en-2-yl benzoate

HRID 2378678ノート

反応式

HRID 2378678 の反応式
[C:1]([O:4][CH2:5][C:6]1[C:11](I)=[CH:10][CH:9]=[C:8]([NH:13][C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[C:7]=1[CH3:21])(=[O:3])[CH3:2].O1CCCC1.C(N(CC)CC)C.[C:34]([O:42][C:43]([C:45]([O:47][CH3:48])=[O:46])=[CH2:44])(=[O:41])[C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1>[Cl-].C([N+](CCCC)(CCCC)CCCC)CCC.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:34]([O:42]/[C:43](/[C:45]([O:47][CH3:48])=[O:46])=[CH:44]\[C:11]1[CH:10]=[CH:9][C:8]([NH:13][C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])=[C:7]([CH3:21])[C:6]=1[CH2:5][O:4][C:1](=[O:3])[CH3:2])(=[O:41])[C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1

参加物

7

反応物 4

HCID 8028TetrahydrofuranHCID 8471TriethylamineHCID 641425Methyl 2-(benzoyloxy)-2-propenoateHCID 534147073-(Tert-butoxycarbonylamino)-6-iodo-2-methylbenzyl acetate

生成物 1

HCID 59732069(Z)-1-(2-(acetoxymethyl)-4-(tert-butoxycarbonylamino)-3-methylphenyl)-3-methoxy-3-oxoprop-1-en-2-yl benzoate収率 95.5%

試薬・触媒・溶媒 2

HCID 70681Tetrabutylammonium Chloride触媒HCID 167845palladium(II) acetate触媒

実験手順

3-(tert-butoxycarbonylamino)-6-iodo-2-methylbenzyl acetate (18.0 g, 44.4 mmol) in tetrahydrofuran (180.00 ml, 2197 mmol) was added triethylamine (24.76 ml, 178 mmol) followed by tetrabutylammonium chloride, hydrate (13.15 g, 44.4 mmol) and 3-methoxy-3-oxoprop-1-en-2-yl benzoate (11.91 g, 57.7 mmol). After introducing nitrogen atmosphere, palladium(II) acetate (0.898 g, 4.0 mmol) was added. The reaction mixture was refluxed for 3 h. The crude product was cooled and most of the solvent was removed. The crude product was diluted with ether (300 mL) and solids were removed by filtration. The solvent was evaporated and the crude product was purified by flash chromatography using 30% EtOAc in hexane to 50% EtOAc in hexane. The product was crystallized from a mixture of EtOAc-hexane to give a white powder of (Z)-1-(2-(acetoxymethyl)-4-(tert-butoxycarbonylamino)-3-methylphenyl)-3-methoxy-3-oxoprop-1-en-2-yl benzoate (20.5 g, 42.4 mmol, 95% yield). 1H NMR (500 MHz, CDCl3): in δ 8.08-8.06 (m, 2H), 7.75-7.74 (m, 2H), 7.60-7.58 (m, 1H), 7.49-7.44 (m, 3H), 5.25 (s, 2H), 3.85 (m, 3H), 2.24 (s, 3H), 2.07 (s, 3H), 1.52 (s, 9H); MS (ESI) 506 (M+H); Rf=2.61.

後処理

  1. additionwas added
  2. temperatureThe reaction mixture was refluxed for 3 h
  3. customwas removed
  4. additionThe crude product was diluted with ether (300 mL) and solids
  5. customwere removed by filtration
  6. customThe solvent was evaporated
  7. customthe crude product was purified by flash chromatography
  8. customThe product was crystallized from a mixture of EtOAc-hexane

出典と根拠

ORDレコード
ord-7570e266fa16430d8e2436c4aa581f09
出典データセット
uspto-grants-2008_12
特許番号
US07470679B2

反応ノート

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