The direct synthetic organic use of electricity is currently experiencing a renaissance. More synthetically oriented laboratories working in this area are exploiting both novel and more traditional concepts, paving the way to broader applications of this niche technology. As only electrons serve as reagents, the generation of reagent waste is efficiently avoided. Moreover, stoichiometric reagents can be regenerated and allow a transformation to be conducted in an electrocatalytic fashion. However, the application of electroorganic transformations is more than minimizing the waste footprint, it rather gives rise to inherently safe processes, reduces the number of steps of many syntheses, allows for milder reaction conditions, provides alternative means to access desired structural entities, and creates intellectual property (IP) space. When the electricity originates from renewable resources, this surplus might be directly employed as a terminal oxidizing or reducing agent, providing an ultra‐sustainable and therefore highly attractive technique. This Review surveys recent developments in electrochemical synthesis that will influence the future of this area.

The use of electricity instead of stoichiometric amounts of oxidizers or reducing agents in synthesis is very appealing for economic and ecological reasons, and represents a major driving force for research efforts in this area. To use electron transfer at the electrode for a successful transformation in organic synthesis, the intermediate radical (cation/anion) has to be stabilized. Its combination with other approaches in organic chemistry or concepts of contemporary synthesis allows the establishment of powerful synthetic methods. The aim in the 21st Century will be to use as little fossil carbon as possible and, for this reason, the use of renewable sources is becoming increasingly important. The direct conversion of renewables, which have previously mainly been incinerated, is of increasing interest. This Review surveys many of the recent seminal important developments which will determine the future of this dynamic emerging field.

Simply by applying electricity, the amination reaction of a broad variety of arenes, heteroarenes, and benzylic substrates is achieved. Pyridine serves as the nitrogen source and the intermediate cationic species are well-protected from over-oxidation.

Die direkte Nutzung von Elektrizität für die organische Synthese erlebt derzeit eine Renaissance. Von den eher syntheseorientierten Laboratorien, die auf diesem Gebiet arbeiten, werden neuartige oder althergebrachte Konzepte genutzt, um den Weg von der Nischentechnologie zu breiteren Anwendungen zu ebnen. Da nur Elektronen als Reagens genutzt werden, wird die Bildung von Abfallreagentien effizient vermieden. Darüber hinaus können stöchiometrische Reagentien regeneriert werden und ermöglichen eine elektrokatalysierte Umsetzung. Die Anwendung von elektroorganischen Transformationen ist jedoch mehr als nur die Minimierung des Abfallaufkommens; sie führt vielmehr zu inhärent sicheren Prozessen, zur Abkürzung vieler Synthesestufen, zu milderen Reaktionsbedingungen, zu alternativen Zugängen zu gewünschten Struktureinheiten sowie zur Schaffung neuer Bereiche für geistiges Eigentum (Patente). Wenn die verwendete Elektrizität aus regenerativen Ressourcen stammt, kann dieser Stromüberschuss direkt als terminales Oxidations‐ oder Reduktionsmittel eingesetzt werden, was eine äußerst nachhaltige und damit hochattraktive Technologie darstellt. Dieser Aufsatz gibt einen Überblick über die jüngsten Entwicklungen auf dem Gebiet der elektrochemischen Synthese, welche die Zukunft dieses stark aufstrebenden Gebietes beeinflussen werden.

The anodic C–H amination of aromatic compounds is a powerful and versatile method for the synthesis of aniline derivatives. By using boron‐doped diamond (BDD) anodes, a method initially described by Yoshida et al. for electron‐rich arenes was expanded to less‐activated aromatic systems e.g., simple alkylated benzene derivatives. Anodes based on sp3 carbon seem to be the key for the electrochemical amination reaction. The corresponding primary anilines are obtained in good yields. Despite the cationic intermediates of the electrolytic reaction tert‐butyl moieties are tolerated.