Efficient Synthetic Protocols in Glycerol under Heterogeneous Catalysis

The massive increase in glycerol production from the transesterification of vegetable oils has stimulated a large effort to find novel uses for this compound. Hence, the use of glycerol as a solvent for organic synthesis has drawn particular interest. Drawbacks of this green and renewable solvent are a low solubility of highly hydrophobic molecules and a high viscosity, which often requires the use of a fluidifying co‐solvent. These limitations can be easily overcome by performing reactions under high‐intensity ultrasound and microwaves in a stand‐alone or combined manner. These non‐conventional techniques facilitate and widen the use of glycerol as a solvent in organic synthesis. Glycerol allows excellent acoustic cavitation even at high temperatures (70–100 °C), which is otherwise negligible in water. Herein, we describe three different types of applications: 1) the catalytic transfer hydrogenation of benzaldehyde to benzyl alcohol in which glycerol plays the dual role of the solvent and hydrogen donor; 2) the palladium‐catalyzed Suzuki cross‐coupling; and (3) the Barbier reaction. In all cases glycerol proved to be a greener, less expensive, and safer alternative to the classic volatile organic solvents.