Direct functionalization of unactivated C-H bonds catalyzed by group 3-5 metal alkyl complexes.

This perspective summarizes direct C-H bond functionalization reactions catalyzed by group 3-5 metal alkyl complexes. Metal-carbon bonds of group 3-5 metals have potentially high reactivity toward both C-H bond activation reactions through the intrinsic σ-bond metathesis pathway and insertion of unsaturated organic molecules. Upon the combination of these two elemental steps, direct C-H bond functionalization reactions of (hetero)aromatic compounds, methane, alkylamines, and terminal alkynes, proceed through C(sp)-H, C(sp(2))-H, and C(sp(3))-H bond activation reactions. Here we review as catalysts for these transformations not only simple metallocene complexes but also non-metallocene complexes supported by a variety of ligands, which are often superior in terms of catalyst design and catalytic activity.