Methanol → 6-Methoxy-10-(4-methoxy-phenyl)-1,2,3,4,4a,10a-hexahydro-phenanthren-9-carboxylic acid methyl ester

HRID 418943Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 418943
[CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:14](=[CH:15][CH:16]=1)[C:13](OS(C(F)(F)F)(=O)=O)=[C:12]([C:25]1[CH:30]=[CH:29][C:28]([O:31][CH3:32])=[CH:27][CH:26]=1)[CH:11]1[CH:6]2[CH2:7][CH2:8][CH2:9][CH2:10]1.C1C=CC(P(C2C=CC=CC=2)CCCCP(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CCN(CC)CC.CO.[C:72]([O:75][CH2:76]C)(=[O:74])C>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.CS(C)=O>[CH3:76][O:75][C:72]([C:13]1[C:14]2[C:5]([CH:6]3[CH:11]([C:12]=1[C:25]1[CH:26]=[CH:27][C:28]([O:31][CH3:32])=[CH:29][CH:30]=1)[CH2:10][CH2:9][CH2:8][CH2:7]3)=[CH:4][C:3]([O:2][CH3:1])=[CH:16][CH:15]=2)=[O:74]

Komponenten

8

Edukt 5

HCID 887MethanolHCID 8471TriethylamineHCID 8857Ethyl AcetateHCID 821241,4-Bis(diphenylphosphino)butaneHCID 72309400Trifluoro-methanesulfonic acid 6-methoxy-10-(4-methoxy-phenyl)-1,2,3,4,4a,10a-hexahydro-phenanthren-9-yl ester

Produkt 1

HCID 666519606-Methoxy-10-(4-methoxy-phenyl)-1,2,3,4,4a,10a-hexahydro-phenanthren-9-carboxylic acid methyl esterAusbeute 63 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 167845palladium(II) acetateKatalysatorHCID 679Dimethyl SulfoxideLösungsmittel

Versuchsvorschrift

Combine trifluoro-methanesulfonic acid 6-methoxy-10-(4-methoxy-phenyl)-1,2,3,4,4a,10a-hexahydro-phenanthren-9-yl ester (19.83 g, 42.3 mmol), palladium acetate (1.93 g), dppb (4.58 g), Et3N (60.0 mL), methanol (265 mL), and DMSO (400.0 mL), and stir under 100 psi of CO atmosphere at 80° C. After 18 hours, add ethyl acetate and wash the ethyl acetate 5× with brine, then dry the organic phase with anhydrous sodium sulfate and concentrate. Flash chromatograph using 5% to 30% ethyl acetate/hexanes to yield the titled compound (10.06 g, 63%) as a pinkish-white solid. TLC Rf=0.25 in 6:1 hexanes:ethyl acetate. 1H NMR (CDCl3): 7.31 (m, 2H), 7.25 (d, 1H, J=8.4 Hz), 6.92 (m, 3H), 6.76 (dd, 1H, J=8.6, 2.4 Hz), 3.86 (m, 6H), 3.60 (s, 3H), 3.25 (d, 1H, J=4.4 Hz), 2.70 (m, 1H), 2.40 (m, 1H), 1.75 (m, 1H), 1.53 (m, 4H), 1.31 (m, 2H).

Aufarbeitung

  1. washwash the ethyl acetate 5× with brine
  2. dry with materialdry the organic phase with anhydrous sodium sulfate
  3. concentrationconcentrate

Quellen und Nachweise

ORD-Eintrag
ord-f9ba617e1fb6427792990d3eed129837
Quelldatensatz
uspto-grants-2012_01
Patentnummer
US08093302B2

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