Electrosynthesis is a popular, green alternative to traditional organic methods. Understanding the mechanisms is not trivial yet is necessary to optimize reaction processes. To this end, a multitude of analytical tools is available to identify and quantitate reaction products and intermediates. The first portion of this review serves as a guide that underscores electrosynthesis fundamentals, including instrumentation, electrode selection, impacts of electrolyte and solvent, cell configuration, and methods of electrosynthesis. Next, the broad base of analytical techniques that aid in mechanism elucidation are covered in detail. These methods are divided into electrochemical, spectroscopic, chromatographic, microscopic, and computational. Technique selection is dependent on predicted reaction pathways and electrogenerated intermediates. Often, a combination of techniques must be utilized to ensure accuracy of the proposed model. To conclude, future prospects that aim to enhance the field are discussed.

Vitamin B 12 derivatives catalyze a wide range of organic transformations, but B 12 -dependent enzymes are underutilized in biocatalysis relative to other metalloenzymes. In this study, we engineered a variant of the transcription factor CarH, called CarH*, that catalyzes styrene C−H alkylation with improved yields (2−6.5-fold) and selectivity relative to cobalamin. While the native function of CarH involves transcription regulation via adenosylcobalamin (AdoCbl) Co(III)−carbon bond cleavage and β-hydride elimination to generate 4′,5′-didehydroadenosine, CarH*-catalyzed styrene alkylation proceeds via non-native oxidative addition and olefin addition coupled with a native-like β-hydride elimination. Mechanistic studies on this reaction echo findings from earlier studies on AdoCbl homolysis to suggest that CarH* selectivity results from its ability to impart a cage effect on radical intermediates. These findings lay the groundwork for the development of B 12 -dependent enzymes as catalysts for non-native transformations.

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Cyclic voltammetry and controlled‐potential (bulk) electrolysis have been used to study the direct electrochemical reduction of cyclohexyl bromide (1) and cyclohexyl iodide (2) at glassy carbon cathodes in dimethylformamide (DMF) containing 0.10 M tetramethylammonium tetrafluoroborate (TMABF4). Direct reduction of 1 is a one‐step process that affords a carbanion intermediate, whereas 2 undergoes stepwise reduction to a radical and then a carbanion intermediate. Mixtures of cyclohexane, cyclohexene, and bicyclohexyl arise from bulk electrolyses of both 1 and 2. Catalytic reduction of 1 and 2 by nickel(I) salen and cobalt(I) salen electrogenerated at glassy carbon cathodes in DMF‐TMABF4 has been investigated with the aid of both cyclic voltammetry and bulk electrolysis. Products arising from these catalytic reductions are cyclohexane, cyclohexene, and bicyclohexyl, although significant amounts of unreduced 1 are found when cobalt(I) salen is utilized as the catalyst. Mechanistic aspects of the direct and catalyzed reductions of 1 and 2 are discussed.