Mechanistic Investigation on Potassium Amide-Catalyzed Benzylic C–H Bond Addition of Alkylpyridines to Styrenes

The catalytic C–H bond addition of alkylpyridines to olefins represents one of the most efficient approaches to alkyl-substituted pyridine derivatives with 100% atom-economy efficiency. Various catalysts including late transition metal, early transition metal, and s-block metal complexes displayed rich and versatile activity. Potassium amide could selectively achieve the benzylic alkylation of alkylpyridines, displaying distinct activity and regioselectivity. Here, the mechanistic investigation via both kinetic experiments and DFT calculations revealed the dimer structure of potassium amide and confirmed alkylation via a kinetic deprotonative functionalization process.