Green chemistry and flow chemistry are ideal partners for accessing novel chemical spaces and define highly efficient synthetic tools.

γ-Valerolactone (GVL) is an excellent reaction medium, derived from biomasses, which can replace classic dipolar aprotic media such as DMF or NMP.

γ-Valerolactone (GVL) can be used as an efficient and practical alternative to the banned and commonly used dipolar aprotic solvents.

γ-Valerolactone (GVL) can be a valid biobased replacement for toxic dipolar aprotic solvents especially in widely used cross-coupling reactions. In this contribution, we have proved that GVL can be a useful medium for the Hiyama reaction, and we developed a practical and efficient protocol for the Hiyama coupling using a nonexpensive and commercially available heterogeneous palladium catalyst without the use of any ligand or additive. Desired cross-coupling products 3a−m have been obtained in good to excellent yields (74−94%).

A highly sustainable and waste-minimized protocol for Heck coupling has been defined. Optimal conditions have been defined by exploiting a heterogeneous catalyst based on supported ionic liquid-like phases featuring high Pd loading (10 wt %) and by optimizing its efficiency in a recoverable green reaction medium (acetonitrile/water azeotrope). Pure products 4a–l and 6a–h have been isolated chromatography-free in high yields (74–99%) and with extremely low environmental factor (E-factor) values (2.3–5.0). With the application of flow technology, the selected heterogeneous base and Pd catalyst have been fully recovered and reused, and minimum palladium leaching allowed for isolation of the final products with low residual palladium content (<5 ppm) without any purification step