Allyltributylstannane → 5-Allylisoquinoline

HRID 1793194Notes

Reaction equation

HRID 1793194 reaction equation
Br[C:2]1[CH:11]=[CH:10][CH:9]=[C:8]2[C:3]=1[CH:4]=[CH:5][N:6]=[CH:7]2.[CH2:12]([Sn](CCCC)(CCCC)CCCC)[CH:13]=[CH2:14].[F-].[K+]>C1(C)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.Cl[Pd]Cl>[CH2:14]([C:2]1[CH:11]=[CH:10][CH:9]=[C:8]2[C:3]=1[CH:4]=[CH:5][N:6]=[CH:7]2)[CH:13]=[CH2:12]

Participants

6

Reactant 3

HCID 90628AllyltributylstannaneHCID 522689Potassium FluorideHCID 7364875-Bromoisoquinoline

Product 1

HCID 220259635-AllylisoquinolineYield 92%

Reagents, catalysts & solvents 2

HCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 1140TolueneSolvent

Procedure

5-Bromoisoquinoline (Preparation 6, Step 1, 1.04 g, 5.0 mmol) was mixed with allyltributyltin (1.7 mL, 5.5 mmol) and dichloropalladium bis(triphenylphosphine) (176 mg, 0.25 mmol) in toluene (20 mL) under a nitrogen atmosphere. The mixture was heated at reflux for 16 h. After cooling to room temperature, a saturated aqueous solution of potassium fluoride (20 mL) was added with stirring, resulting in the formation of a precipitate. Following 15 min of stirring, the mixture was filtered and the organic layer was separated from the aqueous layer, was concentrated in vacuo and was purified by silica gel chromatography (6:1 hexanes-ethyl acetate) to give 778 mg (92% yield) of 5-allylisoquinoline; 1H NMR (400 MHz, CDCl3) δ 9.25 (s, 1H), 8.54 (d, J=5.8 Hz, 1H), 7.85 (m, 1H), 7.79 (d, J=5.8 Hz, 1H), 7.56 (m, 2H), 6.1 (m, 1H), 5.15 (m, 1H), 5.05 (m, 1H), 3.81 (d, J=6.2 Hz, 2H); MS (AP/CI): 170.1 (M+H)+.

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux for 16 h
  3. customresulting in the formation of a precipitate
  4. stirringof stirring
  5. filtrationthe mixture was filtered
  6. customthe organic layer was separated from the aqueous layer
  7. concentrationwas concentrated in vacuo
  8. customwas purified by silica gel chromatography (6:1 hexanes-ethyl acetate)

Sources & evidence

ORD record
ord-45852c4d4052420286b592d39aa1fdb0
Source dataset
uspto-grants-2006_07
Patent number
US07078529B2

Reaction notes

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