This review summarizes the most recent advances of metal-free late-stage functionalization (LSF) of pharmaceutically relevant molecules. Particular emphasis is placed on C–H activation as well as the use of endogenous functional groups.

A light-driven pinacol coupling protocol without any metals, but with N2H4 as a clean non-metallic hydrogen-atom-transfer (HAT) reductant was described.

EDA complexes with catalytic triarylamines allow C–H perfluoroalkylation of arenes and heteroarenes under visible light irradiation in pH- and redox-neutral conditions. A detailed photophysical characterization of the EDA complex is provided.