Allyltributylstannane → HCID 118307146, compound

HRID 921249Notes

Reaction equation

HRID 921249 reaction equation
Br[C:2]1[CH:11]=[C:10]([F:12])[C:9]([F:13])=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].[CH2:14]([Sn](CCCC)(CCCC)CCCC)[CH:15]=[CH2:16].[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>[CH2:16]([C:2]1[CH:11]=[C:10]([F:12])[C:9]([F:13])=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5])[CH:15]=[CH2:14]

Participants

7

Reactant 3

HCID 90628AllyltributylstannaneHCID 433294Lithium ChlorideHCID 26985845Methyl 2-bromo-4,5-difluorobenzoate

Product 1

HCID 118307146HCID 118307146, compoundYield 78.1%

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolventHCID 6342AcetonitrileSolvent

Conditions

Temperature
90 °C

Procedure

A mixture of methyl 2-bromo-4,5-difluorobenzoate (0.5 g, 1.992 mmol), allyltributylstannane (0.679 mL, 2.191 mmol), lithium chloride (0.169 g, 3.98 mmol) in DMF (1 mL), acetonitrile (10 mL) was added bis(triphenylphosphine)palladium(ii) dichloride (0.070 g, 0.100 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 for 5 times, then 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-4,5-difluorobenzoate (330 mg, 1.555 mmol, 78% yield) as an oil. 1H NMR (400 MHz, CDCl3) 7.78 (dd, J=11.1, 8.2 Hz, 1H), 7.11 (dd, J=11.1, 7.7 Hz, 1H), 5.98 (ddt, J=16.9, 10.2, 6.5 Hz, 1H), 5.16-5.02 (m, 2H), 3.91 (s, 3H), 3.76 (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 for 5 times
  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-d4356c5ebb7f4c8787e30e4408d8a797
Source dataset
uspto-grants-2016_03
Patent number
US09273067B2

Reaction notes

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