Tetrahydrofuran → 6-Methoxy-10-(4-methoxy-phenyl)-9-methyl-1,2,3,4,4a,10a-hexahydro-phenanthrene

HRID 418954Notes

Reaction equation

HRID 418954 reaction equation
[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.O1CCC[CH2:34]1.C[Zn]C.C(OCC)(=O)C>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O>[CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:14](=[CH:15][CH:16]=1)[C:13]([CH3:34])=[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

Participants

7

Reactant 4

HCID 8028TetrahydrofuranHCID 8857Ethyl AcetateHCID 72309400Trifluoro-methanesulfonic acid 6-methoxy-10-(4-methoxy-phenyl)-1,2,3,4,4a,10a-hexahydro-phenanthren-9-yl esterHCID 178477796HCID 178477796, compound

Product 1

HCID 666520386-Methoxy-10-(4-methoxy-phenyl)-9-methyl-1,2,3,4,4a,10a-hexahydro-phenanthreneYield 60%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent

Procedure

Combine trifluoro-methanesulfonic acid 6-methoxy-10-(4-methoxy-phenyl)-1,2,3,4,4a,10a-hexahydro-phenanthren-9-yl ester (0.523 g, 1.12 mmol), Pd-tetrakis (45.0 mg, 0.04 mmol), and tetrahydrofuran (10.0 mL), and stir under nitrogen atmosphere at 0° C. After 15 minutes, add dimethylzinc (3.5 mL, 3.44 mmol) dropwise. Allow the reaction to warm to room temperature and stir for 18 hours, then heat reaction at 40° C. for 3 hours. Add ethyl acetate and water. Wash the organic phase with brine, dry over anhydrous sodium sulfate, concentrate, and chromatograph eluting with 0% to 20% ethyl acetate/hexanes to yield the titled compound (0.224 g, 60%) as a white solid. TLC Rf=0.30 in 5:1 hexanes:ethyl acetate. 1H NMR (CDCl3): 7.32 (s, 1H), 7.20 (d, 2H, J=8.8 Hz), 6.95 (m, 3H), 6.79 (m, 1H), 3.88 (m, 6H), 3.21 (m, 1H), 2.46 (m, 2H), 1.97 (s, 3H), 1.74 (m, 1H), 1.55 (m, 3H), 1.38 (m, 1H), 1.15 (m, 2H).

Workup

  1. customthe reaction
  2. temperatureheat
  3. customreaction at 40° C. for 3 hours
  4. washWash the organic phase with brine
  5. dry with materialdry over anhydrous sodium sulfate
  6. concentrationconcentrate
  7. washchromatograph eluting with 0% to 20% ethyl acetate/hexanes

Sources & evidence

ORD record
ord-cb037b8cbe774a27a9e5525ac26206ae
Source dataset
uspto-grants-2012_01
Patent number
US08093302B2

Reaction notes

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