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

HRID 418943ノート

反応式

HRID 418943 の反応式
[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]

参加物

8

反応物 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

生成物 1

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

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 679Dimethyl Sulfoxide溶媒

実験手順

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).

後処理

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

出典と根拠

ORDレコード
ord-f9ba617e1fb6427792990d3eed129837
出典データセット
uspto-grants-2012_01
特許番号
US08093302B2

反応ノート

読み込み中…