Tributylvinyltin → HCID 23310894, compound
Reaction equation
Br[C:2]1[CH:9]=[CH:8][C:5]([CH2:6][OH:7])=[C:4]([CH3:10])[CH:3]=1.[CH:11]([Sn](CCCC)(CCCC)CCCC)=[CH2:12].[F-].[K+]>C1(C)C=CC=CC=1.CCOC(C)=O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:10][C:4]1[CH:3]=[C:2]([CH:11]=[CH2:12])[CH:9]=[CH:8][C:5]=1[CH2:6][OH:7]Participants
Conditions
- Temperature
- 110 °C
Procedure
A solution of 4-bromo-2-methylbenzyl alcohol (M. I. Dawson, et al., J. Med. Chem. 1984, 27, 1516-1531; 0.81 g, 4.0 mmol) in toluene (10 mL) was charged successively with Pd(PPh3)4 (0.13 g, 0.11 mmol), BHT (few crystals, catalytic), and vinyltributyltin (1.3 mL, 4.4 mmol). The mixture was heated at 110° C. for 3.5 h, cooled, charged with aqueous KF and stirred for 12 h at RT. The mixture was diluted with EtOAc and the resultant white precipitate was removed via filtration. The organic phase was separated, dried (Na2SO4), filtered, and concentrated in vacuo. The residue was purified via flash chromatography to afford 2-methyl-4-vinylbenzyl alcohol (0.54 g). A portion (0.27 g) of this product in methylene chloride (5 mL) was added to a precooled (−78 ° C.) mixture of oxalyl chloride (1.3 mL, 2.6 mmol) and DMSO (0.3 mL, 4.3 mmol) in methylene chloride (10 mL). The reactoin was charged with triethylamine (1.0 mL, 7.2 mmol) and stirred in the cold bath for 2 h, at which point the bath was at RT. The reaction was stirred for an additional hour at RT and then quenched with sat.
Workup
- temperaturecooled
- customthe resultant white precipitate was removed via filtration
- customThe organic phase was separated
- dry with materialdried (Na2SO4)
- filtrationfiltered
- concentrationconcentrated in vacuo
- customThe residue was purified via flash chromatography
Sources & evidence
- ORD record
- ord-53eb56b50a0d4d519c849bb04b55f020
- Source dataset
- uspto-grants-2008_11
- Patent number
- US07449493B2
Reaction notes
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