Periphery‐Arranged Bulky Phosphite Ligand for Nickel‐Catalyzed Suzuki–Miyaura Cross‐Coupling of 2‐Chloropyridines

ABSTRACT

In Ni‐catalyzed Suzuki–Miyaura cross‐coupling, achieving high catalytic efficiency is often hampered by the formation of inactive nickel off‐cycle species coordinated by heteroatoms. This issue is particularly pronounced with 2‐chloropyridines, which tend to generate stable dimeric off‐cycle complexes. We herein report the application of periphery‐arranged bulky phosphite ligands to the Ni‐catalyzed Suzuki–Miyaura cross‐coupling of 2‐chloropyridines. These ligands exhibit higher efficiency than conventional phosphites. Furthermore, mechanistic investigations and density functional theory (DFT) calculations elucidate the steric effects of these ligands in suppressing catalyst deactivation and promoting the catalytic cycle.