A method to introduce allyl or cinnamyl groups to the picolyl positions of 2- or 4-alkylpyridines is described. Substituted N-allyl pyridinium salts are first treated with base (KOtBu) followed by catalytic [(η3-allyl)PdCl]2 and PPh3 to result in formal Pd-catalyzed transfer of N-allyl groups to the pyridine periphery. The reaction is believed to proceed through initial formation of nucleophilic alkylidene dihydropyridine intermediates that react with (π-allyl)Pd(II) electrophiles, thereby regenerating N-allyl pyridinium cations. Catalytic turnover and liberation of pyridine products is then achieved by oxidative addition of Pd(0) to these activated allyl groups.
Keywords: Allylation; Catalysis; Dihydropyridine; Palladium; Pyridine.