Tris(4-fluorophenyl)phosphine → 4-Chloro-5-nitro-1H-pyrrolo[2,3-b]pyridine

HRID 1969813Notes

Reaction equation

HRID 1969813 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]=12

Participants

5

Reactant 2

HCID 140387Tris(4-fluorophenyl)phosphineHCID 585573334-Chloro-3-ethynyl-5-nitropyridin-2-amine

Product 1

HCID 585572594-Chloro-5-nitro-1H-pyrrolo[2,3-b]pyridineYield 82.5%

Reagents, catalysts & solvents 2

HCID 6436379Rhodium, di-mu-chlorobis((1,2,5,6-eta)-1,5-cyclooctadiene)di-CatalystHCID 6228DimethylformamideSolvent

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 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

  1. customThe reaction mixture was degassed
  2. customby bubbling argon for 15 min
  3. customThe solvent was removed under reduced pressure
  4. filtrationThe precipitate was collected by filtration
  5. customdried

Sources & evidence

ORD record
ord-33bb91a3350a438d9fce68122d1e8481
Source dataset
uspto-grants-2013_04
Patent number
US08426411B2

Reaction notes

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