Stannane, tributyl(1-ethoxyethenyl)- → 1-[5-Hydroxy-1-(phenylsulfonyl)-1H-indol-4-yl]ethanone

HRID 2423171Notes

Reaction equation

HRID 2423171 reaction equation
C([O:4][C:5]1[C:6](Br)=[C:7]2[C:11](=[CH:12][CH:13]=1)[N:10]([S:14]([C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)(=[O:16])=[O:15])[CH:9]=[CH:8]2)(=O)C.[CH2:24]([O:26]C([Sn](CCCC)(CCCC)CCCC)=C)[CH3:25]>C1(C)C=CC=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl>[OH:4][C:5]1[C:6]([C:24](=[O:26])[CH3:25])=[C:7]2[C:11](=[CH:12][CH:13]=1)[N:10]([S:14]([C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1)(=[O:15])=[O:16])[CH:9]=[CH:8]2

Participants

5

Reactant 2

HCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 672413314-Bromo-1-(phenylsulfonyl)-1H-indol-5-yl acetate2×

Product 1

HCID 672421721-[5-Hydroxy-1-(phenylsulfonyl)-1H-indol-4-yl]ethanoneYield 21.1%

Reagents, catalysts & solvents 2

HCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
110 °C

Procedure

4-Bromo-1-(phenylsulfonyl)-1H-indol-5-yl acetate (Intermediate 22, 0.57 g, 1.5 mmol) was dissolved in toluene (10 mL) under an atmosphere of N2 gas and 1-ethoxyvinyl-tributylstannane (0.78 g, 2.2 mmol) and bis-(triphenylphosphin)-palladium(II)-chloride (50.8 mg, 0.072 mmol) were added and the mixture was heated at 110° C. After 30 minutes additional catalyst (25 mg, 0.036 mmol) was added and the mixture was heated at 110° C. for an additional 3 hours, cooled and filtered through a plug of silica gel using EtOAc as the eluent. The filtrate was washed with 1 M HCl and saturated aqueous brine, dried over (MgSO4) and evaporated. The crude product was dissolved in THF/1 M HCl 2:1 (40 mL) and stirred for 30 minutes at room temperature. The mixture was evaporated and partitioned between water and DCM. The organic phase was dried (MgSO4) and evaporated. The crude material was purified by flash chromatography on silica gel using 10% petroleum ether in DCM as the eluent to give the title compound (100 mg) as a light yellow solid. MS m/z 316 [M+H]+.

Workup

  1. temperaturethe mixture was heated at 110° C. for an additional 3 hours
  2. temperaturecooled
  3. filtrationfiltered through a plug of silica gel
  4. washThe filtrate was washed with 1 M HCl and saturated aqueous brine
  5. dry with materialdried over (MgSO4)
  6. customevaporated
  7. dissolutionThe crude product was dissolved in THF/1 M HCl 2:1 (40 mL)
  8. customThe mixture was evaporated
  9. custompartitioned between water and DCM
  10. dry with materialThe organic phase was dried (MgSO4)
  11. customevaporated
  12. customThe crude material was purified by flash chromatography on silica gel using 10% petroleum ether in DCM as the eluent

Sources & evidence

ORD record
ord-93412b1cc5ae4b3cac7a56dd20ce2d8d
Source dataset
uspto-grants-2011_06
Patent number
US07960374B2

Reaction notes

Loading…