title: Palladium-Catalyzed Aerobic Acetoxylation of Benzene using NOx-Based Redox Mediators.
abstract: Palladium-catalyzed methods for C-H oxygenation with O2as the stoichiometric oxidant are limited. Here, we describe the use of nitrite and nitrate sources as NOx-based redox mediators in the acetoxylation of benzene. The conditions completely avoid formation of biphenyl as a side product, and strongly favor formation of phenyl acetate over nitrobenzene (PhOAc:PhNO2ratios up to 40:1). Under the optimized reaction conditions, with 0.1 mol% Pd(OAc)2, 136 turnovers of Pd are achieved with only 1 atm of O2pressure.
authors.affiliation: Department of Chemistry, University of Wisconsin-Madison, 1101 University Ave., Madison, Wisconsin 53706, United States.
authors.forename: Susan L
authors.initials: SL
authors.lastname: Zultanski
authors.affiliation: Department of Chemistry, University of Wisconsin-Madison, 1101 University Ave., Madison, Wisconsin 53706, United States.
authors.forename: Shannon S
authors.initials: SS
authors.lastname: Stahl
keywords: C–H activation; aerobic; benzene; nitrate; nitric acid; nitrite; oxidation; palladium; phenol; phenyl acetate; redox mediators
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