Tributylvinyltin → 2-vinyl-7,8-dihydroquinolin-5(6H)-one

HRID 1506409Notes

Reaction equation

HRID 1506409 reaction equation
FC(F)(F)S(O[C:7]1[CH:16]=[CH:15][C:14]2[C:13](=[O:17])[CH2:12][CH2:11][CH2:10][C:9]=2[N:8]=1)(=O)=O.[CH2:20]([Sn](CCCC)(CCCC)C=C)[CH2:21]CC.[Cl-].[Li+]>O1CCOCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH:20]([C:7]1[CH:16]=[CH:15][C:14]2[C:13](=[O:17])[CH2:12][CH2:11][CH2:10][C:9]=2[N:8]=1)=[CH2:21]

Participants

6

Reactant 3

HCID 81998TributylvinyltinHCID 433294Lithium ChlorideHCID 866698985-Oxo-5,6,7,8-tetrahydroquinolin-2-yl trifluoromethanesulfonate

Product 1

HCID 671675322-vinyl-7,8-dihydroquinolin-5(6H)-oneYield 84%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Procedure

To a solution of 5-oxo-5,6,7,8-tetrahydroquinolin-2-yl trifluoromethanesulfonate (Preparation 54B, 2.21 g, 7.49 mmol) in dioxane (12 mL) in a sealed tube was added sequentially tributyl(vinyl)stannane (2.418 mL, 8.23 mmol) and lithium chloride (0.952 g, 22.46 mmol). The mixture was degassed under reduced pressure and charged with nitrogen (3×). To the mixture was added tetrakis(triphenylphosphine)palladium(0) (0.865 g, 0.749 mmol), and the mixture was stirred under a strong stream of nitrogen for 5 min. The reaction mixture was sealed, immersed in an oil bath at 100° C., and stirred overnight. The reaction mixture was filtered and the solid was rinsed with ethyl acetate (150 mL). The filtrate was concentrated under reduced pressure, and the resulting residue was diluted with ether (150 mL). The resulting solid was removed by vacuum filtration and rinsed with ether (150 mL). The filtrate was concentrated under reduced pressure and purified by flash silica gel chromatography using a mixture of ethyl acetate in hexane (5%-12.5%-20%) to give 2-vinyl-7,8-dihydroquinolin-5(6H)-one (1.09 g, 6.29 mmol, 84% yield) as a pale yellow solid. The compound had an HPLC ret. time=0.738 min. (condition A); LC/MS M+1=273.8; 1H NMR (500 MHz, CDCl3) δ ppm 2.21 (quin, 2H), 2.67-2.73 (m, 2H), 3.15 (t, J=6.10 Hz, 2H), 5.65 (d, J=10.82 Hz, 1H), 6.35 (d, J=17.48 Hz, 1H), 6.86 (dd, J=17.48, 10.54 Hz, 1H), 7.34 (d, J=8.05 Hz, 1H), and 8.25 (d, J=8.05 Hz, 1H).

Workup

  1. customThe mixture was degassed under reduced pressure
  2. additioncharged with nitrogen (3×)
  3. customThe reaction mixture was sealed
  4. customimmersed in an oil bath at 100° C.
  5. stirringstirred overnight
  6. filtrationThe reaction mixture was filtered
  7. washthe solid was rinsed with ethyl acetate (150 mL)
  8. concentrationThe filtrate was concentrated under reduced pressure
  9. additionthe resulting residue was diluted with ether (150 mL)
  10. customThe resulting solid was removed by vacuum filtration
  11. washrinsed with ether (150 mL)
  12. concentrationThe filtrate was concentrated under reduced pressure
  13. custompurified by flash silica gel chromatography
  14. additiona mixture of ethyl acetate in hexane (5%-12.5%-20%)

Sources & evidence

ORD record
ord-feec7f1ec0f54fa99c5c4bce2302ed46
Source dataset
uspto-grants-2015_12
Patent number
US09216972B2

Reaction notes

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