The C-H functionalization of organic cations: an interesting and fresh journey.

Organic ionic compounds, especially those with organic cations, are commonly applied in ionic liquids (ILs), organocatalysts, (a)NHC ligands, ion recognition, and optoelectronic materials. The direct C-H functionalization of organic cations offers valuable opportunities for the rapid assembly of diverse functionalized cations and for their further exploitation in material science applications. This review summarizes the substantial progress that has been made in the C-H functionalization of organic cations from the 1960s to May 2020, including transition metal-mediated/catalyzed C-H alkylation, arylation, and annulation, and photo-induced C-H functionalization. Substrate scopes, limitations, regio-/chemoselectivity, and reaction mechanisms are discussed. In addition, the applications of some new organic functional materials are briefly exemplified. This review also aims to serve as a reminder that much care should be taken when using organic ionic compounds as solvents, because they can behave as reactants that can break up desired coupling reactions.