Electroorganic Synthesis and the Construction of Addressable Molecular Surfaces

In this Minireview, an electroorganic synthesis approach to the construction of addressable, complex molecular surfaces is described along with the parameters that guided the development of that synthetic approach. The result of the work is a synthetic toolbox that will allow microelectrode arrays to be used for the “real‐time” monitoring of small molecule interactions with […]

Paired Electrochemical Reactions and the On‐Site Generation of a Chemical Reagent

While the majority of reported paired electrochemical reactions involve carefully matched cathodic and anodic reactions, the precise matching of half reactions in an electrolysis cell is not generally necessary. During a constant current electrolysis almost any oxidation and reduction reaction can be paired, and in the presented work we capitalize on this observation by examining […]

Organic Electrochemistry and a Role Reversal: Using Synthesis To Optimize Electrochemical Methods

Diblock copolymers are excellent coatings for microelectrode arrays because they provide a stable surface that can support both synthetic and analytical electrochemistry. However, the surfaces that are optimal for synthetic studies are not the same as the surfaces that are optimal for analytical studies. Hence, no one surface provides an ideal platform for both building […]

Anodic Cyclization Reactions and the Mechanistic Strategies That Enable Optimization

Oxidation reactions are powerful tools for synthesis because they allow us to reverse the polarity of electron-rich functional groups, generate highly reactive intermediates, and increase the functionality of molecules. For this reason, oxidation reactions have been and continue to be the subject of intense study. Central to these efforts is the development of mechanism-based strategies […]

Insights into the Mechanism of Anodic N-N Bond Formation by Dehydrogenative Coupling

The electrochem. synthesis of pyrazolidine-3,5-diones and benzoxazoles by N-N bond formation and C,O linkage, resp., represents an easy access to medicinally relevant structures.  Electrochem. as a key technol. ensures a safe and sustainable approach.  We gained insights in the mechanism of these reactions by combining cyclovoltammetric and synthetic studies.  The electron-transfer behavior of anilides and […]

Electrochemical synthesis of benzoxazoles from anilides – a new approach to employ amidyl radical intermediates

A novel electrochemical method for the synthesis of benzoxazoles from readily available anilides is reported. Various functionalities are tolerated and good yields can be achieved. By employing common electrode materials and a simple constant current protocol, this method is an attractive new alternative to conventional pathways. Tile Gieshoff, Anton Kehl, Dieter Schollmeyer, Kevin D. Moeller […]

Paired Electrolysis in the Simultaneous Production of Synthetic Intermediates and Substrates

In electrochem. processes, an oxidn. half-reaction is always paired with a redn. half-reaction.  Although systems for reactions such as the redn. of CO2 can be coupled to H2O oxidn. to produce O2 at the anode, large-scale O2 prodn. is of limited value.  One may replace a low-value half-reaction with a compatible half-reaction that can produce […]