This review describes the most recent developments in materials design and the advanced features of ionogels, as well as their emerging biomedical applications.

Copper-catalyzed olefinic trifluoromethylation and oxytrifluoromethylation of enamides is reported. The direct olefinic C–H trifluoromethylation constitutes an efficient method for the stereoselective synthesis of β-trifluoromethyl substituted enamides.

Fluoroalkenes represent a class of privileged structural motifs, which found widespread use in medicinal chemistry. However, the synthetic access to fluoroalkenes was much underdeveloped with previous reported methods suffering from either low step economy or harsh reaction conditions. Here we present a Rh^III-catalysed tandem C–H/C–F activation for the synthesis of (hetero)arylated monofluoroalkenes. The use of readily availablegem-difluoroalkenes as electrophiles provides a highly efficient and operationally simple method for the introduction of α-fluoroalkenyl motifs onto (hetero)arenes under oxidant-free conditions. Furthermore, the employment of alcoholic solvent and thein-situgenerated hydrogen fluoride are found to be beneficial in this transformation, indicating the possibility of the involvement of hydrogen bond activation mode with regards to the C–F bond cleavage step.

Chemoselective functionalization of intrinsically less reactive C(sp3)–H bonds of alkyl nitriles are of particular interest to the chemical community in view that these strategies provide opportunities for the introduction of important cyanoalkyl groups onto target frameworks in a step-economic fashion. In recent years, the introduction of nitrile-containing alkyl radicals in tandem radical additions and oxidative couplings inarguably brings chemists a new radical reaction platform for the diverse synthesis of natural products and pharmaceuticals. Compared with the wide applications of various C-centred radicals adjacent to a heteroatom, however, the nitrile-containing alkyl radicals remain largely unexplored. New methods for C(sp3)−H bond oxidative functionalization of alkyl nitriles and new mechanistic manifolds would result in the development of a broad range of novel reactions. Therefore, this review will give an overview of various types of radical cyanoalkylation by using the key alkyl nitrile reactants, which is beyond traditional coupling chemistry.