HCID 90203845, compound → HCID 90203632, compound

HRID 1480216Notes

Reaction equation

HRID 1480216 reaction equation
Cl[C:2]1[CH:7]=[C:6]([Cl:8])[C:5]([CH:9]2[CH2:11][CH2:10]2)=[CH:4][N:3]=1.[C:12]([Zn]C#N)#[N:13]>CN(C=O)C.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.[Fe+2].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]>[Cl:8][C:6]1[C:5]([CH:9]2[CH2:11][CH2:10]2)=[CH:4][N:3]=[C:2]([C:12]#[N:13])[CH:7]=1

Participants

6

Reactant 2

HCID 90203845HCID 90203845, compoundHCID 178514179HCID 178514179, compound

Product 1

HCID 90203632HCID 90203632, compoundYield 73.2%

Reagents, catalysts & solvents 3

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

To a stirred solution of 2,4-dichloro-5-cyclopropyl-pyridine (example 145a, 2.2 g, 11.76 mmol) in DMF (10 ml) and purged the reaction mixture argon for 10 minutes. To this reaction was added dicyanozinc (926 mg, 7.65 mmol) followed by DPPF (520 mg, 1.02 mmol) and Pd2dba3 (535 mg, 0.58 mmol) at 25° C. and the reaction mixture was again purged with argon for 10 min. The reaction mixture was heated up to 100° C. for 1 hour. The catalyst was filtered off and the solution was diluted with ethyl acetate. The organic phase was poured into a separatory funnel and extracted with brine. The organic phase was dried over sodium sulfate and concentrated under reduced pressure. The crude material was purified by flash chromatography on silica eluting with a heptane/ethyl acetate gradient to yield the title compound (1 g, 50%). MS (ESI, m/z): 179.2 (M+H+).

Workup

  1. customthe reaction mixture was again purged with argon for 10 min
  2. filtrationThe catalyst was filtered off
  3. additionthe solution was diluted with ethyl acetate
  4. additionThe organic phase was poured into a separatory funnel
  5. extractionextracted with brine
  6. dry with materialThe organic phase was dried over sodium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customThe crude material was purified by flash chromatography on silica eluting with a heptane/ethyl acetate gradient

Sources & evidence

ORD record
ord-6254611aed0c49ffb3278978323708ac
Source dataset
uspto-grants-2016_08
Patent number
US09409866B2

Reaction notes

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