Methoxytri-n-butylstannane → (8R,9S,13S,14S)-13-ethyl-3-methoxy-7,8,9,11,12,14-hexahydro-6H-cyclopenta[a]phenanthren-17-one

HRID 1650116Notes

Reaction equation

HRID 1650116 reaction equation
C([O:4][C:5]1[C@:6]2([CH2:23][CH2:22][C@H:21]3[C@@H:12]([CH2:13][CH2:14][C:15]4[CH:16]=[C:17]([O:24][CH3:25])[CH:18]=[CH:19][C:20]=43)[C@@H:9]2[CH2:10][CH:11]=1)[CH2:7][CH3:8])(=O)C.C(COC(=O)[O-])C=C.C[O-].C([Sn+](CCCC)CCCC)CCC>C(#N)C.O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:25][O:24][C:17]1[CH:18]=[CH:19][C:20]2[C@@H:21]3[C@H:12]([C@H:9]4[C@@:6]([CH2:23][CH2:22]3)([CH2:7][CH3:8])[C:5](=[O:4])[CH:11]=[CH:10]4)[CH2:13][CH2:14][C:15]=2[CH:16]=1

Participants

7

Reactant 3

HCID 11964040Methoxytri-n-butylstannaneHCID 14257187(13S)-Ethyl-3-methoxygona-1,3,5(10),16-tetraen-17-ol AcetateHCID 23349072Allylmethyl carbonate

Product 1

HCID 14257189(8R,9S,13S,14S)-13-ethyl-3-methoxy-7,8,9,11,12,14-hexahydro-6H-cyclopenta[a]phenanthren-17-one

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 6342AcetonitrileSolvent

Procedure

3.4 g of 17-acetoxy-3-methoxy-18-methyl-1,3,5(10),16-estratetraene is refluxed for 1.5 hours in 50 ml of acetonitrile with 2.3 ml of allylmethylcarbonate, 220 mg of palladium acetate and 580 microliters of tributyltin methoxide. The reaction mix is then diluted with water, extracted with dichloromethane and concentrated under vacuum. After chromatographic purification, 2.1 g of 3-methoxy-18-methyl-1,3,5(10),15-estratetraen-17-one with a melting point of 158°-160° C. is obtained.

Workup

  1. additionThe reaction mix
  2. extractionextracted with dichloromethane
  3. concentrationconcentrated under vacuum
  4. customAfter chromatographic purification, 2.1 g of 3-methoxy-18-methyl-1,3,5(10),15-estratetraen-17-one with a melting point of 158°-160° C.
  5. customis obtained

Sources & evidence

ORD record
ord-95a999309b8c4483b9256bf1acf92cda
Source dataset
uspto-grants-1990_05
Patent number
US04923640

Reaction notes

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