Tributylvinyltin → HCID 23310894, compound

Participants

Reaction Conditions

Reaction Steps

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. NaHCO3. The mixture was extracted with EtOAc (2×), and the organic phase was dried (Na2SO4), filtered, and concentrated in vacuo to afford pure 2-methyl-4-vinylbenzaldehyde.

Provenance & Evidence