Allyltributylstannane → HCID 57443291, compound

HRID 921233Notes

Reaction equation

HRID 921233 reaction equation
Br[C:2]1[CH:11]=[C:10]([CH3:12])[CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].[CH2:13]([Sn](CCCC)(CCCC)CCCC)[CH:14]=[CH2:15].[Cl-].[Li+]>CN(C=O)C.C(#N)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH2:15]([C:2]1[CH:11]=[C:10]([CH3:12])[CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5])[CH:14]=[CH2:13]

Participants

7

Reactant 3

HCID 90628AllyltributylstannaneHCID 433294Lithium ChlorideHCID 21779704Methyl 2-bromo-4-methylbenzoate

Product 1

HCID 57443291HCID 57443291, compoundYield 79.5%

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolventHCID 6342AcetonitrileSolvent

Conditions

Temperature
90 °C

Procedure

A mixture of methyl 2-bromo-4-methylbenzoate (500 mg, 2.183 mmol), allyltributylstannane (0.744 mL, 2.401 mmol), lithium chloride (185 mg, 4.37 mmol) in DMF (1 mL), acetonitrile (10 mL) was added bis(triphenylphosphine)palladium(ii) dichloride (77 mg, 0.109 mmol). It was then degassed for 2 min, then filled with N2. After heating at 90° C. for 16 h, it was quenched with NH4Cl, extracted with EtOAc. The organic layer was washed with KF solution, dried over MgSO4, filtered and concentrated to obtain an oil, which was then purified by biotage, eluting with 10% EtOAc/hexane to isolate methyl 2-allyl-4-methylbenzoate (330 mg, 1.735 mmol, 79% yield) as an oil. 1H NMR (400 MHz, CDCl3) δ 7.95-7.77 (m, 1H), 7.21-6.99 (m, 2H), 6.19-5.85 (m, 1H), 5.22-4.91 (m, 2H), 3.89 (s, 3H), 3.76 (d, J=6.6 Hz, 2H), 2.39 (s, 3H).

Workup

  1. customIt was then degassed for 2 min
  2. additionfilled with N2
  3. customit was quenched with NH4Cl
  4. extractionextracted with EtOAc
  5. washThe organic layer was washed with KF solution
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customto obtain an oil, which
  10. customwas then purified by biotage
  11. washeluting with 10% EtOAc/hexane

Sources & evidence

ORD record
ord-1284b90736c242108e291465ec2fdbaa
Source dataset
uspto-grants-2016_03
Patent number
US09273067B2

Reaction notes

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