TY - JOUR
T1 - Organic Oxidations Using Geomimicry
AU - Yang, Ziming
AU - Hartnett, Hilairy
AU - Shock, Everett
AU - Gould, Ian
N1 - Funding Information:
The authors acknowledge helpful discussions with the members of the Hydrothermal Organic Geochemistry (H.O.G.) group at Arizona State University. We are thankful for National Science Foundation Grant OCE-1357243 for the financial support.
PY - 2015/11/12
Y1 - 2015/11/12
N2 - 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.
AB - 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.
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U2 - 10.1021/acs.joc.5b02109
DO - 10.1021/acs.joc.5b02109
M3 - Article
AN - SCOPUS:84952803327
SN - 0022-3263
VL - 80
SP - 12159
EP - 12165
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 24
ER -