Azaindoles and azaindolines are important core structures in pharmaceuticals and natural products, which have found wide applications in the field of medicinal chemistry. In this study, we developed a novel one-pot method for selectively synthesizing 7-azaindoles and 7-azaindolines, which can be generated by reactions between the readily available 2-fluoro-3-methylpyridine and arylaldehydes. The chemoselectivity is counterion dependent, with LiN(SiMe3)2 generating 7-azaindolines and KN(SiMe3)2 furnishing 7-azaindoles. A range of substituents can be introduced under these conditions, providing handles for further elaboration and functionalization.
