Ligand-Modulated Palladium-Catalyzed Aerobic Alcohol Oxidations

The discovery and investigation of ligand-modulated Pd-catalyzed aerobic alcohol oxidations is documented. The project has evolved from a simple empirical discovery that (-)-sparteine, in combination with Pd(II) salts, facilitates the aerobic oxidative kinetic resolution of secondary alcohols to an in-depth physical organic investigation that has provided key insights into how new, more effective catalysts can be designed. Mechanistic investigations, the substrate scope for the catalysts developed, and implications to oxidation catalysis are discussed.