Exploring Electrosynthesis: Bulk Electrolysis and Cyclic Voltammetry Analysis of the Shono Oxidation.

As electrochemistry continues to gain broader acceptance and use within the organic chemistry community, it is important that advanced undergraduate students are exposed to fundamental and practical knowledge of electrochemical applications for chemical synthesis. Herein, we describe the development of an undergraduate laboratory experience that introduces synthetic and analytical electrochemistry concepts to an advanced organic chemistry class. Experiments focus on the electrooxidative α-functionalization of carbamates, more generally known as the Shono oxidation, and include cyclic voltammetry analysis of two cyclic carbamates and a constant current bulk electrolysis reaction. The exercise offers students an authentic experience in organic electrochemistry, lays a practical and theoretical foundation for future engagement with concepts in electrochemistry and redox chemistry, and strengthens fundamental organic chemistry skills.

"How Should I Think about Voltage? What Is Overpotential?": Establishing an Organic Chemistry Intuition for Electrochemistry.

Redox reactions are ubiquitous in organic synthesis and intrinsic to organic electrosynthesis. The language and concepts used to describe reactions in these domains are sufficiently different to create barriers that hinder broader adoption and understanding of electrochemical methods. To bridge these gaps, this Synopsis compares chemical and electrochemical redox reactions, including concepts of free energy, voltage, kinetic barriers, and overpotential. This discussion is intended to increase the accessibility of electrochemistry for organic chemists lacking formal training in this area.

Deriving the Turnover Frequency of Aminoxyl-Catalyzed Alcohol Oxidation by Chronoamperometry: An Introduction to Organic Electrocatalysis.

Organic electrosynthesis is an increasingly popular tool for driving and probing redox reactions. Recent advances in this field often employ an electrocatalyst to enhance the selectivity and efficiency of electrochemical reactions. A laboratory experiment was developed to introduce students to relevant mechanistic techniques in electrochemistry for analysis of electrocatalytic reactions using aminoxyl-catalyzed alcohol oxidation as a case study. This lab activity employs cyclic voltammetry for qualitative assessment of catalytic turnover prior to introducing students to chronoamperometry, an underutilized technique that facilitates quantitative determination of the rate of catalysis. Students identify and rationalize the important features of reversible electron transfer and a catalytic reaction in a cyclic voltammogram, probe the origin of scan rate effects on these traces, and calculate turnover frequency using a series of chronoamperograms. The method employs safe and readily available reagents: basic aqueous buffer solution, alcohol substrate, and an inexpensive organic aminoxyl catalyst. Student data presented herein were obtained from a course attended by undergraduate students, graduate students, and pharmaceutical chemists.

Iron(III) Nitrate/TEMPO-Catalyzed Aerobic Alcohol Oxidation: Distinguishing between Serial versus Integrated Redox Cooperativity.

Aerobic alcohol oxidations catalyzed by transition metal salts and aminoxyls are prominent examples of cooperative catalysis. Cu/aminoxyl catalysts have been studied previously and feature "integrated cooperativity", in which CuII and the aminoxyl participate together to mediate alcohol oxidation. Here we investigate a complementary Fe/aminoxyl catalyst system and provide evidence for "serial cooperativity", involving a redox cascade wherein the alcohol is oxidized by an in situ-generated oxoammonium species, which is directly detected in the catalytic reaction mixture by cyclic step chronoamperometry. The mechanistic difference between the Cu- and Fe-based catalysts arises from the use iron(III) nitrate, which initiates a NOx-based redox cycle for oxidation of aminoxyl/hydroxylamine to oxoammonium. The different mechanisms for the Cu- and Fe-based catalyst systems are manifested in different alcohol oxidation chemoselectivity and functional group compatibility.

Electrochemical C-H oxygenation and alcohol dehydrogenation involving Fe-oxo species using water as the oxygen source.

High-valent iron-oxo complexes are key intermediates in C-H functionalization reactions. Herein, we report the generation of a (TAML)Fe-oxo species (TAML = tetraamido macrocyclic ligand) via electrochemical proton-coupled oxidation of the corresponding (TAML)FeIII-OH2 complex. Cyclic voltammetry (CV) and spectroelectrochemical studies are used to elucidate the relevant (TAML)Fe redox processes and determine the predominant (TAML)Fe species present in solution during bulk electrolysis. Evidence for iron(iv) and iron(v) species is presented, and these species are used in the electrochemical oxygenation of benzylic C-H bonds and dehydrogenation of alcohols to ketones.

Tetramethylpiperidine N-Oxyl (TEMPO), Phthalimide N-Oxyl (PINO), and Related N-Oxyl Species: Electrochemical Properties and Their Use in Electrocatalytic Reactions.

N-Oxyl compounds represent a diverse group of reagents that find widespread use as catalysts for the selective oxidation of organic molecules in both laboratory and industrial applications. While turnover of N-oxyl catalysts in oxidation reactions may be accomplished with a variety of stoichiometric oxidants, N-oxyl reagents have also been extensively used as catalysts under electrochemical conditions in the absence of chemical oxidants. Several classes of N-oxyl compounds undergo facile redox reactions at electrode surfaces, enabling them to mediate a wide range of electrosynthetic reactions. Electrochemical studies also provide insights into the structural properties and mechanisms of chemical and electrochemical catalysis by N-oxyl compounds. This review provides a comprehensive survey of the electrochemical properties and electrocatalytic applications of aminoxyls, imidoxyls, and related reagents, of which the two prototypical and widely used examples are 2,2,6,6-tetramethylpiperidine N-oxyl (TEMPO) and phthalimide N-oxyl (PINO).

Selective electrochemical generation of benzylic radicals enabled by ferrocene-based electron-transfer mediators.

The generation and intermolecular functionalisation of carbon-centred radicals has broad potential synthetic utility. Herein, we show that benzylic radicals may be generated electrochemically from benzylboronate derivatives at low electrode potentials (ca. -0.3 V vs. Cp2Fe0/+) via single electron oxidation. Use of a catalytic quantity of a ferrocene-based electron-transfer mediator is crucial to achieve successful radical functionalisation and avoid undesirable side reactions arising from direct electrochemical oxidation or from the use of stoichiometric ferrocenium-based oxidants.