Enabling Base‐Free Direct C–H Arylation of Thiophene Derivatives: Glycerol‐Derived Solvents as Active Reaction Media

Nonvolatile glycerol derivatives are employed as effective reaction media for the Pd-catalysed direct C-H arylation of 3,4-ethylenedioxythiophene and other thiophenes. The thoughtful design of noninnocent glycerol-derived ionic liquids (ILs) allows them to act simultaneously both as solvent and base, eliminating the need for an additional base and thus improving the sustainability of the process. Moreover, the stabilization of palladium nanoparticles in the task-specific solvent offers an excellent approach by providing the advantages of a homogeneous, selective, and recoverable catalytic system. This multifunctional behaviour highlights the potential of glycerol-derived ILs as sustainable solvents and promoters for transition metal-catalysed C-H activation reactions.