Tris(4-fluorophenyl)phosphine → 4-Chloro-5-nitro-1H-pyrrolo[2,3-b]pyridine
Reaction equation
[Cl:1][C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][N:5]=[C:4]([NH2:11])[C:3]=1[C:12]#[CH:13].FC1C=CC(P(C2C=CC(F)=CC=2)C2C=CC(F)=CC=2)=CC=1>CN(C=O)C.C1CC=CCCC=C1.C1CC=CCCC=C1.[Cl-].[Cl-].[Rh].[Rh]>[Cl:1][C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][N:5]=[C:4]2[NH:11][CH:13]=[CH:12][C:3]=12Participants
Reactant 2
Product 1
Reagents, catalysts & solvents 2
Conditions
- Temperature
- 80 °C
Procedure
To a solution of 4-chloro-3-ethynyl-5-nitropyridin-2-amine (0.16 g, 0.81 mmol) in DMF (3 mL) was added chloro(1,5-cyclooctadiene) rhodium (I) dimer (0.02 g, 0.04 mmol) and tris(4-fluorophenyl)phosphine (0.128 g, 0.405 mmol). The reaction mixture was degassed by bubbling argon for 15 min. The reaction mixture was heated at about 80° C. for about 45 min. The reaction was cooled to ambient temperature and the solvent was removed under reduced pressure and the residue was suspended in ether (10 mL). The precipitate was collected by filtration and dried to give 4-chloro-5-nitro-1H-pyrrolo[2,3-b]pyridine (0.132 g, 83%, contains approximately 6% mol of DMF and approximately 3% mol of tris(4-fluorophenyl)phosphine) as a brown solid: LC/MS (Table 1, Method a) Rt=2.05 min; MS m/z 198 (M+H)+.
Workup
- customThe reaction mixture was degassed
- customby bubbling argon for 15 min
- temperatureThe reaction was cooled to ambient temperature
- customthe solvent was removed under reduced pressure
- filtrationThe precipitate was collected by filtration
- customdried
Sources & evidence
- ORD record
- ord-c38b59bbe4224b64bc212677605f405a
- Source dataset
- uspto-grants-2013_04
- Patent number
- US08426411B2
Reaction notes
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