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

HRID 418943노트

반응식

HRID 418943 반응식
[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]

참가 물질

8

반응물 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

생성물 1

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

시약·촉매·용매 2

HCID 167845palladium(II) acetate촉매HCID 679Dimethyl Sulfoxide용매

실험 절차

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).

후처리

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

출처 및 근거

ORD 기록
ord-f9ba617e1fb6427792990d3eed129837
출처 데이터셋
uspto-grants-2012_01
특허 번호
US08093302B2

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