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

HRID 2378902Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2378902
[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

Komponenten

7

Edukt 4

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

Produkt 1

HCID 59732069(Z)-1-(2-(acetoxymethyl)-4-(tert-butoxycarbonylamino)-3-methylphenyl)-3-methoxy-3-oxoprop-1-en-2-yl benzoateAusbeute 95,5 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 70681Tetrabutylammonium ChlorideKatalysatorHCID 167845palladium(II) acetateKatalysator

Versuchsvorschrift

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.

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-e06d9087915d4398834460bb1d13ef07
Quelldatensatz
uspto-grants-2008_12
Patentnummer
US07470680B2

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