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Palladium(II)-catalyzed allylic acetoxylation has been the focus of extensive development and investigation. Methods that use molecular oxygen (O 2 ) 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 Pd 0 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 O 2 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) O 2 alone, (2) O 2 with cocatalytic BQ, and (3) O 2 with cocatalytic BQ and Co(salophen). The beneficial effect of BQ in the absence of Co(salophen) is traced to synergistic roles of O 2 and BQ, both of which are capable of oxidizing Pd 0 to Pd II The reaction of O 2 generates H 2 O 2 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., Competing Interests: The authors declare no competing financial interests.

The title compound, [RuCl2(C10H14)(C14H15OP)], is an Ru(II) complex in which an η(6)-p-cymene ligand, two chloride anions and the P atom of an ethoxydiphenylphosphane ligand form a piano-stool coordination environment about the central Ru(II) atom.