Palladium-catalyzed allylation of 2- and 4-alkylpyridines via N-allyl alkylidene dihydropyridine intermediates.

ABSTRACT: 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 (KO^tBu) 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.

SUBMITTER: Shivers GN 

PROVIDER: S-EPMC10569290 | biostudies-literature | 2023 Sep

REPOSITORIES: biostudies-literature