Transition metal catalyzed cross-coupling reactions are powerful methods to forge new C–C and C–X bonds in large part due to the design of ligands that have enabled novel reactivity. These developments are especially evident in Pd chemistry, where entire ligand libraries have been developed specifically to engender reactivity in mechanistically well-understood Pd cross-coupling reactions. In contrast, while many ligand classes have been identified as effective in Ni catalysis, less is known about what factors govern their reactivity. Herein, we study electron-deficient olefin ligands that have shown unique reactivity for Ni. We show mechanistic and computational studies that shed light on the mechanisms of fundamental steps in Ni catalysis. These studies have elucidated the role of electron-deficient olefin ligands in promoting the reactivity of these steps. Based on this investigation, we highlight features of the ligand class and catalytic system that are necessary for reactivity. These features will have important implications for the design of ligands uniquely suited for Ni catalysis to refine known reactivity and access novel methods.

Design principles for electron-deficient olefin ligands in Ni catalysis

ACS Spring 2022

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