Acetate → HCID 44211033, compound

HRID 650416Notes

Reaction equation

HRID 650416 reaction equation
C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:30][O:31][C:32]1[CH:37]=[CH:36][C:35]([CH:38]2[C:46]3[C:41](=[CH:42][CH:43]=[C:44]([O:47][CH2:48][CH2:49][CH3:50])[CH:45]=3)[CH:40]([C:51]3[CH:56]=[CH:55][C:54]4[O:57][CH2:58][O:59][C:53]=4[CH:52]=3)[CH:39]2[C:60]([O-:62])=[O:61])=[C:34](OS(C(F)(F)F)(=O)=O)[CH:33]=1.[C:71]([O:75]C)(=[O:74])[CH:72]=[CH2:73].C([O-])(=O)C>C(N(CC)CC)C.C(#N)C.CN(C=O)C.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].[Pd]>[C:71](/[CH:72]=[CH:73]/[C:34]1[CH:33]=[C:32]([O:31][CH3:30])[CH:37]=[CH:36][C:35]=1[CH:38]1[C:46]2[C:41](=[CH:42][CH:43]=[C:44]([O:47][CH2:48][CH2:49][CH3:50])[CH:45]=2)[CH:40]([C:51]2[CH:56]=[CH:55][C:54]3[O:57][CH2:58][O:59][C:53]=3[CH:52]=2)[CH:39]1[C:60]([OH:62])=[O:61])([OH:75])=[O:74]

Participants

9

Reactant 4

HCID 175AcetateHCID 7294Methyl Acrylate2×HCID 812191,3-Bis(diphenylphosphino)propaneHCID 21713099HCID 21713099, compound

Product 1

HCID 44211033HCID 44211033, compound

Reagents, catalysts & solvents 4

HCID 23938PalladiumCatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 6228DimethylformamideSolventHCID 21895542Acetonitrile triethylamineSolvent

Procedure

1,3-bis(diphenylphosphino)propane (0.066 mmol), tris(dibenzylideneacetone)-dipalladium(0) (24 mg, 0.026) and bis(triphenylphosphine)palladium(II) choride (18 mg, 0.026 mmol), were dissolved in a 4:1 mixture of triethylamine/acetonitrile (5 mL) under argon. After 10 min at room temperature, a solution of methyl (1RS, 2SR, 3RS)-3-(4-methoxy-2-trifluoromethanesulfonyloxyphenyl)-1-(3,4-methylenedioxyphenyl)-5-(prop-1-yloxy)indane-2-carboxylate (160 mg, 0.26 mmol) and methyl acrylate (679 mg, 7.89 mmol) was added in the above solvent mixture (3 mL). The reaction mixture was heated to reflux under argon for 20 h, cooled to room temperature and a small aliquot analyzed by 1H NMR, which showed no reaction had taken place. Palladium(l) acetate (6 mg, 0.025 mmol) and methyl acrylate (679 mg, 7.89 mmol) in dry DMF (5 mL) were then added. The reaction mixture was heated to reflux overnight. On cooling the solution was filtered through a short column of silica gel and concentrated to yield an oil. The crude product was purified by flash column chromatography ( silica gel, gradient elution: 10% to 20% ethyl acetate/hexanes) to afford the title compound as a tan solid. (87 mg, 62%).

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureto reflux under argon for 20 h
  3. temperatureThe reaction mixture was heated
  4. temperatureto reflux overnight
  5. temperatureOn cooling the solution
  6. filtrationwas filtered through a short column of silica gel
  7. concentrationconcentrated
  8. customto yield an oil
  9. customThe crude product was purified by flash column chromatography ( silica gel, gradient elution: 10% to 20% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-007f3a477145488095844fdccdf1e1f0
Source dataset
uspto-grants-2001_08
Patent number
US06271399B1

Reaction notes

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