Electrochemistry represents one of the most intimate ways of interacting with molecules. This review discusses advances in synthetic organic electrochemistry since 2000. Enabling methods and synthetic applications are analyzed alongside innate advantages as well as future challenges of electroorganic chemistry.

Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

Arylated products are found in various fields of chemistry and represent essential entities for many applications. Therefore, the formation of this structural feature represents a central issue of contemporary organic synthesis. By the action of electricity the necessity of leaving groups, metal catalysts, stoichiometric oxidizers, or reducing agents can be omitted in part or even completely. The replacement of conventional reagents by sustainable electricity not only will be environmentally benign but also allows significant short cuts in electrochemical synthesis. In addition, this methodology can be considered as inherently safe. The current survey is organized in cathodic and anodic conversions as well as by the number of leaving groups being involved. In some electroconversions the reagents used are regenerated at the electrode, whereas in other electrotransformations free radical sequences are exploited to afford a highly sustainable process. The electrochemical formation of the aryl–substrate bond ...

Electrochemical Arylation Reaction.

Contribution of Electrochemistry to Organometallic Catalysis

Methods for the synthesis of gem-difluoromethylene compounds

Electrochemistry has recently gained increased attention as a versatile strategy for achieving challenging transformations at the forefront of synthetic organic chemistry. Electrochemistry's unique ability to generate highly reactive radical and radical ion intermediates in a controlled fashion under mild conditions has inspired the development of a number of new electrochemical methodologies for the preparation of valuable chemical motifs. Particularly, recent developments in electrosynthesis have featured an increased use of redox-active electrocatalysts to further enhance control over the selective formation and downstream reactivity of these reactive intermediates. Furthermore, electrocatalytic mediators enable synthetic transformations to proceed in a manner that is mechanistically distinct from purely chemical methods, allowing for the subversion of kinetic and thermodynamic obstacles encountered in conventional organic synthesis. This review highlights key innovations within the past decade in the area of synthetic electrocatalysis, with emphasis on the mechanisms and catalyst design principles underpinning these advancements. A host of oxidative and reductive electrocatalytic methodologies are discussed and are grouped according to the classification of the synthetic transformation and the nature of the electrocatalyst.

Electrocatalysis as an enabling technology for organic synthesis.

Conjugate addition reaction of heteroaryl halides to activated olefins has been successfully achieved by nickel catalysis combined with the consumable anode procedure and provides access to various functionalized hetertoaryl compounds with potential biological activity.

Nickel Catalyzed Electrochemical Heteroarylation of Activated Olefins

Mn(III)-Mediated electrochemical C,C-bond formation: radical addition of polyhalomethanes to olefins

A stepwise procedure allowing the formation of symmetrical arylphosphines is described. It relies on the use of preformed functionalized aromatic organozinc reagents to perform arylations of chlorophosphines. Some preliminary results concerning the synthesis of unsymmetrical diarylphenylphosphines through sequential coupling of organozinc species with dichlorophenylphosphine are also reported.

Synthesis of Symmetrical and Unsymmetrical Functionalized Arylphosphines from Chlorophosphines and Organozinc Reagents

A process for the preparation of chiral 2-aryl or 2-heterocyclyl-propionic acids of the formula wherein the substituents are as defined in the specification.

Method for preparing 2-aryl or 2-heterocyclyl chiral propionic acids and their esters

The electroreductive coupling of activated olefins and 1–3 dibromide reported in a previous paper leads to a cyclic product when the reaction is carried out in an undivided cell in NMP and in the presence of a sacrificial aluminum anode, but not in a divided cell A mechanistic study has been made to explain the discrepancy between the two methods. We report here that in the undivided cell and in the presence of anodically generated aluminum ions the electroreduction of activated olefins mainly lead to a dianion, while a radical anion is the main reactive species under the other experimental conditions.

Isabelle Lachaise

Papers

Nickel Catalyzed Electrochemical Heteroarylation of Activated Olefins

Mn(III)-Mediated electrochemical C,C-bond formation: radical addition of polyhalomethanes to olefins

Synthesis of Symmetrical and Unsymmetrical Functionalized Arylphosphines from Chlorophosphines and Organozinc Reagents

Method for preparing 2-aryl or 2-heterocyclyl chiral propionic acids and their esters

Intermediate and reaction mechanism of the electroreductive coupling of activated olefins and alkyl dihalides using the sacrificial anode process