Allyltributylstannane → HCID 57443291, compound

HRID 2261777Notes

Reaction equation

HRID 2261777 reaction equation
[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[CH:8][C:7]([CH3:10])=[CH:6][C:5]=1Br.[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>[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[CH:8][C:7]([CH3:10])=[CH:6][C:5]=1[CH2:15][CH:14]=[CH2:13]

Participants

7

Reactant 3

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

Product 1

HCID 57443291HCID 57443291, compoundYield 89%

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolventHCID 6342AcetonitrileSolvent

Conditions

Temperature
120 °C

Procedure

To a solution of 2-bromo-4-methyl-benzoic acid methyl ester (1.330 g, 5.81 mmol) in 5 mL DMF and 50 mL acetonitrile are added allyl tri-n-butyl tin (2.12 g, 6.39 mmol), PdCl2(PPh3)2 (0.203 g, 0.29 mmol), and lithium chloride (0.493 g, 11.6 mmol). The resulting mixture is heated to 120° C. for 8 hours. The reaction is cooled to room temperature and concentrated under reduced pressure. The residue is dissolved in dichloromethane and purified via chromatography eluting with 10% ethyl acetate in hexanes to give 0.980 g (89%) of the desired product. 1H NMR (400 MHz, CDCl3) δ 7.79-7.76 (d, 1H), 7.05 (s, 1H), 7.05-7.03 (d, 1H), 6.03-5.92 (m, 1H), 5.01 (dd, 1H), 4.99-4.98 (dd, 1H), 3.84 (s, 3H), 3.72 (dd, 1H), 3.70 (dd, 1H), 2.33 (s, 3H).

Workup

  1. temperatureThe reaction is cooled to room temperature
  2. concentrationconcentrated under reduced pressure
  3. dissolutionThe residue is dissolved in dichloromethane
  4. custompurified via chromatography
  5. washeluting with 10% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-b0d0fefecc70448590d2faab998b4302
Source dataset
uspto-grants-2010_12
Patent number
US07846960B2

Reaction notes

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