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.

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.

Biomass-derived commodity chemical 5-hydroxymethyl furfural is an underutilized C6-platform chemical derived from cellulose that is ideal to prepare next-generation value-added products. We have developed an efficient synthetic strategy to access 2,5-diaryl nonsymmetric furans from 5-hydroxymethyl furfural utilizing decarboxylative cross-couplings. A key finding was that the presence of the hydroxymethyl handle enhances the yields of the palladium-catalyzed decarboxylative cross-coupling reaction. The method provides access to a broad-range nonsymmetric 2,5-diaryl furans where each arene can be systematically introduced as required. Additionally, this green synthetic strategy was employed for a formal synthesis of the muscle relaxant Dantrolene in excellent yields.