Alcohol oxidation is an important class of reaction that is traditionally performed under harsh conditions and most often requires the use of organometallic compounds or transition metal complexes as catalysts. Here, we introduce a new electrochemical synthetic method, referred to as reductive oxidation, in which alcohol oxidation is initiated by the redox-mediated electrocatalytic reduction of peroxydisulfate to generate the highly oxidizing sulfate radical anion. Thus, and counter-intuitively, alcohol oxidation occurs as a result of an electrochemical reduction reaction. This approach provides a selective synthetic route for the oxidation of alcohols carried out under mild conditions to aldehydes, ketones, and carboxylic acids with up to 99% conversion yields. First-principles density functional theory calculations, ab initio molecular dynamics simulations, cyclic voltammetry, and finite difference simulations are presented that support and provide additional insights into the S2O82--mediated oxidation of benzyl alcohol to benzaldehyde.
Bibliographical noteFunding Information:
This work was supported by the National Science Foundation Center for Synthetic Organic Electrochemistry (CHE-2002158). NMR results included in this report were recorded at the David M. Grant NMR Center, a University of Utah Core Facility. A.D.P. acknowledges a National Science Foundation Graduate Research Fellowship (Grant no. 1747505). Funds for construction of the Center and the helium recovery system were obtained from the University of Utah and the National Institutes of Health grants 1C06RR017539-01A1 and 3R01GM063540-17W1, respectively. NMR instruments were purchased with the support of the University of Utah and National Institutes of Health Grant 1S10OD25241-01. M. T. and M. N. acknowledge the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for the computational resources.
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PubMed: MeSH publication types
- Journal Article
- Research Support, U.S. Gov't, Non-P.H.S.
- Research Support, Non-U.S. Gov't
- Research Support, N.I.H., Extramural