Selective C–H activation of pyridine via Ni–Al

Selective C–H bond functionalization of pyridine as a methodology for building complex molecules is of importance in all branches of chemical science. Compared with a more common C–H transformation at the ortho-position, lack of directing groups and electronic stabilization renders remote para-C–H activation of pyridine less accessible. The Ong and Nakao/Hiyama groups independently discovered a catalytic system based on cooperative Ni–Al to achieve para-selective alkenylation/alkylation of pyridine (Scheme A). These works, accompanied by solid-state structural evidence, establish a new platform in selective C–H catalysis based on a cooperative Ni–Al strategy.