Dimethylformamide → 4-Bromo-1-oxo-indan-5-carbonitrile

HRID 2406505Notes

Reaction equation

HRID 2406505 reaction equation
[Br:1][C:2]1[C:10](OS(C(F)(F)F)(=O)=O)=[CH:9][CH:8]=[C:7]2[C:3]=1[CH2:4][CH2:5][C:6]2=[O:19].[CH3:20][N:21](C)C=O>[C-]#N.[C-]#N.[Zn+2].C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2]>[Br:1][C:2]1[C:10]([C:20]#[N:21])=[CH:9][CH:8]=[C:7]2[C:3]=1[CH2:4][CH2:5][C:6]2=[O:19]

Participants

5

Reactant 2

HCID 6228DimethylformamideHCID 86700769HCID 86700769, compound

Product 1

HCID 867007704-Bromo-1-oxo-indan-5-carbonitrile

Reagents, catalysts & solvents 2

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)Catalyst

Conditions

Temperature
70 °C

Procedure

Zn(CN)2 (0.60 g) and 1,1′-bis(diphenylphosphino)-ferrocene (0.92 g) are added to a solution of trifluoro-methanesulfonic acid 4-bromo-1-oxo-indan-5-yl ester (5.90 g) in N,N-dimethylformamide (30 mL) at room temperature. The mixture is purged with Ar for 5 min prior to addition of tris(dibenzylideneacetone)dipalladium(0) (760 mg). The mixture is heated to 70° C. and stirred at this temperature for 1 h. After cooling to room temperature, ethyl acetate is added and the resulting mixture is washed with water and brine. The organic phase is dried (MgSO4) and concentrated. The residue is chromatographed on silica gel (cyclohexane/ethyl acetate 99:1→50:50) to give the title compound. LC (method 2): tR=0.88 min; Mass spectrum (ESI−): m/z=234/236 (Br) [M−H]−.

Workup

  1. customThe mixture is purged with Ar for 5 min
  2. additionto addition of tris(dibenzylideneacetone)dipalladium(0) (760 mg)
  3. temperatureAfter cooling to room temperature
  4. additionethyl acetate is added
  5. washthe resulting mixture is washed with water and brine
  6. dry with materialThe organic phase is dried (MgSO4)
  7. concentrationconcentrated
  8. customThe residue is chromatographed on silica gel (cyclohexane/ethyl acetate 99:1→50:50)

Sources & evidence

ORD record
ord-8a4e2f4f1607431183ea567882332397
Source dataset
uspto-grants-2014_08
Patent number
US08809376B2

Reaction notes

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