General procedure for the synthesis of 3-cyano-4-methylpyridine (112) from 3-cyano-4-methyl-2,6-dichloropyridine (Ref. J. Org. Chem. 1960, 25, 560-564): palladium dichloride (50 mg, 0.3 mmol) was added to a degassed 3-cyano-4-methyl-2,6-dichloropyridine (5.0 g, 27 mmol) and sodium acetate (4.5 g, 55 mmol) in a methanol (100 mL) solution. The reaction mixture was stirred under hydrogen (1 atm) atmosphere for 14 hours at room temperature. After completion of the reaction, the precipitate was filtered and washed with methanol (3 x 20 mL). The filtrates were combined, the solvent was removed by evaporation under reduced pressure and chloroform (50 mL) was added to the residue. The chloroform solution was filtered through a thin silica gel pad and the silica gel pad was washed with additional chloroform. The filtrate was evaporated to dryness to afford 3-cyano-4-methylpyridine (112) (2.9 g, 93% yield) as a yellow oil. The product was characterized by 1H NMR (300 MHz, DMSO-d6): δ 8.77 (s, 1H), 8.63 (s, J = 6.0 Hz, 1H), 7.3 (d, J = 6.0 Hz, 1H), 2.56 (s, 3H). The resulting 3-cyano-4-methylpyridine (112) can be used in subsequent reactions without further purification.
