Palladium-Catalyzed Aerobic Acetoxylation of Benzene using NOx-Based Redox Mediators

Susan L Zultanski; Shannon S Stahl

doi:10.1016/j.jorganchem.2015.03.003

Palladium-Catalyzed Aerobic Acetoxylation of Benzene using NO_x-Based Redox Mediators

J Organomet Chem. 2015 May 1:52:97-102. doi: 10.1016/j.jorganchem.2015.03.003.

Authors

Susan L Zultanski¹, Shannon S Stahl¹

Affiliation

¹ Department of Chemistry, University of Wisconsin-Madison, 1101 University Ave., Madison, Wisconsin 53706, United States.

Abstract

Palladium-catalyzed methods for C-H oxygenation with O₂ as the stoichiometric oxidant are limited. Here, we describe the use of nitrite and nitrate sources as NO_x-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:PhNO₂ ratios 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 O₂ pressure.

Keywords: C–H activation; aerobic; benzene; nitrate; nitric acid; nitrite; oxidation; palladium; phenol; phenyl acetate; redox mediators.

Abstract

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