Highly Active Catalyst for Suzuki–Miyaura Coupling to Form Sterically Demanding Biaryls: Electronic Control of Pd through the Secondary Interaction Using a Buchwald-Type Ligand Bearing a Fluorinated Aryl Ring

To accelerate reductive elimination in Suzuki-Miyaura coupling (SMC) through secondary interactions with a Buchwald-type ligand, a heptafluorotolyl group was introduced into the ligand's structure, guided by DFT calculations. The resulting ligand, HFTPhos, was effective for SMC, enabling the formation of sterically demanding biaryls. The catalyst loading could be reduced to as low as 0.025 mol % for tetra-<i>ortho</i>-substituted biaryls and 0.001 mol % for tri-<i>ortho</i>-substituted biaryls.