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Electroreduction of Aryl Halides through Homo- and Heterogeneous Electron-Transfer Catalysis.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Electroreduction of Aryl Halides through Homo- and Heterogeneous Electron-Transfer Catalysis.
Author:	McKenzie, Eric.
Published:	Ann Arbor : ProQuest Dissertations & Theses, 2022
Description:	286 p.
Notes:	Source: Dissertations Abstracts International, Volume: 84-02, Section: B.
Notes:	Advisor: Jacobson, Stephen C.
Contained By:	Dissertations Abstracts International84-02B.
Subject:	Analytical chemistry.
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=29327610
ISBN:	9798841768807

Electroreduction of Aryl Halides through Homo- and Heterogeneous Electron-Transfer Catalysis.
McKenzie, Eric.

Electroreduction of Aryl Halides through Homo- and Heterogeneous Electron-Transfer Catalysis. - Ann Arbor : ProQuest Dissertations & Theses, 2022 - 286 p.

Source: Dissertations Abstracts International, Volume: 84-02, Section: B.

Thesis (Ph.D.)--Indiana University, 2022.

This item must not be sold to any third party vendors.

Electroorganic synthesis has experienced a gratifying renaissance aimed at providing a greener alternative to traditional synthetic methods. In addition to improved atom economy and control over reaction landscapes, electrochemistry avoids long reaction times and the frequent need of toxic solvents. Electrochemical dehalogenation is of particular interest, as the mechanism of carbon–halogen bond reduction is well understood, thus providing a relatively simple synthetic step. Moreover, various homo- and heterogeneous catalysts can be utilized to drive this reaction at reasonably low potentials. Herein, we describe the catalytic electroreduction of various aryl halides at carbon and silver cathodes in dimethylformamide. The central part of this work focuses on brominated phenols, as many anticancer, antimalarial, and antioxidant natural products contain phenol moieties. In addition to electrosynthetic applications, electrochemical dehalogenation serves as a method of environmental remediation, as many toxic compounds contain carbon–halogen bonds. For instance, halogenated phenols are precursors to carcinogenic dioxins and can often mimic thyroid hormones. The second part of this work investigates the electroreduction of polychlorinated benzenes, which are highlighted on the EPA’s priority pollutant list, by a heterogeneous electron-transfer catalyst. In both cases, cyclic voltammetry was performed to determine the electrochemical behavior of each substrate and assess catalytic performance towards electroreduction. Moreover, controlled-potential (bulk) electrolysis was performed to establish the extent of dehalogenation. Gas chromatography (GC), low- and high-resolution gas chromatography–mass spectrometry (GC–MS), as well as MALDI-TOF were utilized to separate, identify, and quantitate electroreduced products.

ISBN: 9798841768807Subjects--Topical Terms:

708695
Analytical chemistry.
Subjects--Index Terms:

Electrocatalysis

Electroreduction of Aryl Halides through Homo- and Heterogeneous Electron-Transfer Catalysis.
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520 $a Electroorganic synthesis has experienced a gratifying renaissance aimed at providing a greener alternative to traditional synthetic methods. In addition to improved atom economy and control over reaction landscapes, electrochemistry avoids long reaction times and the frequent need of toxic solvents. Electrochemical dehalogenation is of particular interest, as the mechanism of carbon–halogen bond reduction is well understood, thus providing a relatively simple synthetic step. Moreover, various homo- and heterogeneous catalysts can be utilized to drive this reaction at reasonably low potentials. Herein, we describe the catalytic electroreduction of various aryl halides at carbon and silver cathodes in dimethylformamide. The central part of this work focuses on brominated phenols, as many anticancer, antimalarial, and antioxidant natural products contain phenol moieties. In addition to electrosynthetic applications, electrochemical dehalogenation serves as a method of environmental remediation, as many toxic compounds contain carbon–halogen bonds. For instance, halogenated phenols are precursors to carcinogenic dioxins and can often mimic thyroid hormones. The second part of this work investigates the electroreduction of polychlorinated benzenes, which are highlighted on the EPA’s priority pollutant list, by a heterogeneous electron-transfer catalyst. In both cases, cyclic voltammetry was performed to determine the electrochemical behavior of each substrate and assess catalytic performance towards electroreduction. Moreover, controlled-potential (bulk) electrolysis was performed to establish the extent of dehalogenation. Gas chromatography (GC), low- and high-resolution gas chromatography–mass spectrometry (GC–MS), as well as MALDI-TOF were utilized to separate, identify, and quantitate electroreduced products.
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