Soft Fluorination of 4-Alkylpyridines

We report the mild and selective mono- and difluorination of 4-alkylpyridines. The process involves soft-dearomatization of pyridines to the corresponding alkylidene dihydropyridines and treatment with Selectfluor. The reaction tolerates a broad range of functional groups, including those bearing acidic and weak C-H bonds. In addition, selective fluorination of 4-alkylpyridines attached to 2-alkylpyridines and 2-alkylpyrimidines can be achieved in good yields, but a 4-alkylpyridine tethered to a 4-alkylpyrimidine is fluorinated at both heterobenzylic positions.