title: Organic Oxidations Using Geomimicry.
abstract: Oxidations of phenylacetic acid to benzaldehyde, benzyl alcohol to benzaldehyde, and benzaldehyde to benzoic acid have been observed, in water as the solvent and using only copper(II) chloride as the oxidant. The reactions are performed at 250 °C and 40 bar, conditions that mimic hydrothermal reactions that are geochemically relevant. Speciation calculations show that the oxidizing agent is not freely solvated copper(II) ions, but complexes of copper(II) with chloride and carboxylate anions. Measurements of the reaction stoichiometries and also of substituent effects on reactivity allow plausible mechanisms to be proposed. These oxidation reactions are relevant to green chemistry in that they proceed in high chemical yield in water as the solvent and avoid the use of toxic heavy metal oxidizing reagents.
authors.affiliation: The School of Molecular Sciences, Arizona State University , Tempe, Arizona 85287, United States.
authors.forename: Ziming
authors.initials: Z
authors.lastname: Yang
authors.affiliation: The School of Molecular Sciences, Arizona State University , Tempe, Arizona 85287, United States.|School of Earth and Space Exploration, Arizona State University , Tempe, Arizona 85287, United States.
authors.forename: Hilairy E
authors.initials: HE
authors.lastname: Hartnett
authors.affiliation: The School of Molecular Sciences, Arizona State University , Tempe, Arizona 85287, United States.|School of Earth and Space Exploration, Arizona State University , Tempe, Arizona 85287, United States.
authors.forename: Everett L
authors.initials: EL
authors.lastname: Shock
authors.affiliation: The School of Molecular Sciences, Arizona State University , Tempe, Arizona 85287, United States.
authors.forename: Ian R
authors.initials: IR
authors.lastname: Gould