Allyltributylstannane → HCID 118307106, compound

HRID 921238Notes

Reaction equation

HRID 921238 reaction equation
Br[C:2]1[CH:11]=[C:10]([F: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]([F: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 7210837Methyl 2-bromo-4-fluorobenzoate

Product 1

HCID 118307106HCID 118307106, compoundYield 39.6%

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolventHCID 6342AcetonitrileSolvent

Conditions

Temperature
90 °C

Procedure

A mixture of methyl 2-bromo-4-fluorobenzoate (1 g, 4.29 mmol), allyltributylstannane (1.464 mL, 4.72 mmol), lithium chloride (0.364 g, 8.58 mmol) in DMF (1 mL), acetonitrile (10 mL) was added bis(triphenylphosphine)palladium(ii) dichloride (0.151 g, 0.215 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. The residue was purified by biotage, eluting with 10% EtOAc/hexane to isolate methyl 2-allyl-4-fluorobenzoate (330 mg, 1.699 mmol, 39.6% yield) as an white solid. 1H NMR (400 MHz, CDCl3) δ 7.96 (dd, J=8.6, 6.1 Hz, 1H), 7.09-6.87 (m, 2H), 6.01 (ddt, J=16.9, 10.3, 6.6 Hz, 1H), 5.19-4.96 (m, 2H), 3.90 (s, 3H), 3.80 (d, J=6.6 Hz, 2H).

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. customThe residue was purified by biotage
  10. washeluting with 10% EtOAc/hexane

Sources & evidence

ORD record
ord-8d482dd858e34523b4a65fc24c2810a1
Source dataset
uspto-grants-2016_03
Patent number
US09273067B2

Reaction notes

Loading…