Dimethylformamide → HCID 67538520, compound

HRID 2383039Notes

Reaction equation

HRID 2383039 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[CH:8]([CH:12]1[CH2:17][CH2:16][CH2:15][CH2:14][CH2:13]1)[N:7]([C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH2:6][CH2:5]2.[CH3:25][N:26](C=O)C>[C-]#N.[Zn+2].[C-]#N.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.Cl[Pd]Cl.[Fe+2]>[C:25]([C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[CH:8]([CH:12]1[CH2:13][CH2:14][CH2:15][CH2:16][CH2:17]1)[N:7]([C:18]([O:20][C:21]([CH3:24])([CH3:22])[CH3:23])=[O:19])[CH2:6][CH2:5]2)#[N:26]

Participants

5

Reactant 2

HCID 6228DimethylformamideHCID 67536842HCID 67536842, compound

Product 1

HCID 67538520HCID 67538520, compound

Reagents, catalysts & solvents 2

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)Catalyst

Conditions

Temperature
120 °C

Procedure

DMF (20 mL) was added to a mixture of tert-butyl 6-bromo-1-cyclohexyl-3,4-dihydroisoquinoline-2(1H)-carboxylate (1.41 g), zinc cyanide (848 mg), and [1,1′-bis(diphenylphosphino)ferrocene]palladium chloride (535 mg), which was then purged with argon gas. Subsequently, tris(dibenzylideneacetone)dipalladium (458 mg) was added to the mixture which was then stirred at 120° C. under an argon atmosphere for 10 hours. Further, tris(dibenzylideneacetone)dipalladium (200 mg) was added thereto, followed by stirring for 10 hours. The reaction material was filtered through celite, and EtOAc and water were added to the filtrate. The organic layer was collected, washed with water and saturated brine, dried over magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane-EtOAc) to obtain tert-butyl 6-cyano-1-cyclohexyl-3,4-dihydroisoquinoline-2(1H)-carboxylate (361 mg).

Workup

  1. customwas then purged with argon gas
  2. additionSubsequently, tris(dibenzylideneacetone)dipalladium (458 mg) was added to the mixture which
  3. additionFurther, tris(dibenzylideneacetone)dipalladium (200 mg) was added
  4. stirringby stirring for 10 hours
  5. filtrationThe reaction material was filtered through celite, and EtOAc and water
  6. additionwere added to the filtrate
  7. customThe organic layer was collected
  8. washwashed with water and saturated brine
  9. dry with materialdried over magnesium sulfate
  10. filtrationfiltered
  11. concentrationThe filtrate was concentrated under reduced pressure
  12. customThe resulting residue was purified by silica gel column chromatography (hexane-EtOAc)

Sources & evidence

ORD record
ord-bd9642bb3da74743bc437a2e7c698593
Source dataset
uspto-grants-2012_09
Patent number
US08263607B2

Reaction notes

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