Allyltributylstannane → Methyl 4-methyl-3-(2-propen-1-yl)benzoate

HRID 1991016Notes

Reaction equation

Br[C:2]1[CH:3]=[C:4]([CH:9]=[CH:10][C:11]=1[CH3:12])[C:5]([O:7][CH3:8])=[O:6].[CH2:13]([Sn](CCCC)(CCCC)CCCC)[CH:14]=[CH2:15].[Cl-].[Li+]>CN(C=O)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>[CH3:8][O:7][C:5](=[O:6])[C:4]1[CH:9]=[CH:10][C:11]([CH3:12])=[C:2]([CH2:15][CH:14]=[CH2:13])[CH:3]=1

Participants

Conditions

Temperature: 95 °C

Procedure

Argon was bubbled into a solution of methyl 3-bromo-4-methylbenzoate (11.45 g, 50 mmol), allyltributyl-stannane (16.72 g, 50.5 mmol) and lithium chloride (5.30 g, 125 mmol) in DMF (100 mL) with magnetic stirring for 20 minutes. Dichlorobis(triphenyl-phosphine)palladium (0.81 g, 1.16 mmol) was then added and mixture heated at 95° C. for 1.5 hours. After cooling to room temperature, the mixture was partitioned between ether-hexanes (1:1 V/V) and water. The combined organic layers were washed with brine, dried (MgSO4), filtered and concentrated under reduced pressure. The residue was purified by flash chromatography (Isco RediSep 330 g silica gel, 5% then 35% dichloromethane in hexanes) to give 3-allyl-4-methyl-benzoic acid methyl ester (9.68 g, 100%) as a colorless oil.

Workup

temperatureAfter cooling to room temperature
customthe mixture was partitioned between ether-hexanes (1:1 V/V) and water
washThe combined organic layers were washed with brine
dry with materialdried (MgSO4)
filtrationfiltered
concentrationconcentrated under reduced pressure
customThe residue was purified by flash chromatography (Isco RediSep 330 g silica gel, 5%

Sources & evidence

ORD record: ord-1a01e4bda73d4eecab1e40d3e29a28bc
Source dataset: uspto-grants-2010_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07645764B2

Reaction notes

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