Benzoquinone Cocatalyst Contributions to DAF/Pd(OAc)2-Catalyzed Aerobic Allylic Acetoxylation in the Absence and Presence of a Co(salophen) Cocatalyst

Abstract

Palladium(II)-catalyzed allylic acetoxylation has been the focus of extensive development and investigation. Methods that use molecular oxygen (O₂) as the terminal oxidant typically benefit from the use of benzoquinone (BQ) and a transition-metal (TM) cocatalyst, such as Co(salophen), to support oxidation of Pd⁰ during catalytic turnover. We previously showed that Pd(OAc)₂ and 4,5-diazafluoren-9-one (DAF) as an ancillary ligand catalyze allylic oxidation with O₂ in the absence of cocatalysts. Herein, we show that BQ enhances DAF/Pd(OAc)₂ catalytic activity, nearly matching the performance of reactions that include both BQ and Co(salophen). These observations are complemented by mechanistic studies of DAF/Pd(OAc)₂ catalyst systems under three different oxidation conditions: (1) O₂ alone, (2) O₂ with cocatalytic BQ, and (3) O₂ with cocatalytic BQ and Co(salophen). The beneficial effect of BQ in the absence of Co(salophen) is traced to the synergistic roles of O₂ and BQ, both of which are capable of oxidizing Pd⁰ to Pd^II. The reaction of O₂ generates H₂O₂ as a byproduct, which can oxidize hydroquinone to quinone in the presence of Pd^II. NMR spectroscopic studies, however, show that hydroquinone is the predominant redox state of the quinone cocatalyst in the absence of Co(salophen), while inclusion of Co(salophen) maintains oxidized quinone throughout the reaction, resulting in better reaction performance.