Divergent Reaction of Activated Pyridines with α,α-Difluorinated gem-Diols: Regioselective Synthesis of gem-Difluorinated Dihydropyridines and Dihydropyridones

The nucleophilic reactivity of α,α-difluorinated gem-diols toward activated pyridinium salts has been capitalized in a highly regioselective fashion, offering biologically relevant 1,4-dihydropyridines and 3,4-dihydro-2-pyridones adorned with the valuable gem-difluoromethylene motif. The protocol is scalable as well as high yielding and accommodates a broad range of substrates and functional groups. Additionally, the synthesis of difluorinated oxa-azabicyclo[3.3.1]nonane frameworks has been showcased through product diversification.