Ligand-Based Control of Nickel Catalysts: Switching Chemoselectivity from One-Electron to Two-Electron Pathways in Competing Reactions of 4-Halotetrahydropyrans

Development of nickel-catalyzed transformations would be facilitated by an improved ability to predict which ligands promote and suppress competing mechanisms. We evaluate ligand-based modulation of catalyst preference for one- or two-electron pathways employing 4-halotetrahydropyrans as model substrates that can undergo divergent reaction pathways. Chemoselectivity for one- or two-electron oxidative addition is predicted by ligand class. Phosphine-ligated nickel catalysts favor closed-shell oxidative addition. In contrast, nitrogen-ligated nickel catalysts prefer the one-electron pathway, initiating with halogen atom transfer.