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.

Electrifying Organic Synthesis

Ionic liquid crystals.

Biological photosynthesis uses the energy of several visible light photons for the challenging oxidation of water, whereas chemical photocatalysis typically involves only single-photon excitation. Perylene bisimide is reduced by visible light photoinduced electron transfer (PET) to its stable and colored radical anion. We report here that subsequent excitation of the radical anion accumulates sufficient energy for the reduction of stable aryl chlorides giving aryl radicals, which were trapped by hydrogen atom donors or used in carbon-carbon bond formation. This consecutive PET (conPET) overcomes the current energetic limitation of visible light photoredox catalysis and allows the photocatalytic conversion of less reactive chemical bonds in organic synthesis.

http://science.sciencemag.org/content/sci/346/6210/725.full.pdf

Reduction of aryl halides by consecutive visible light-induced electron transfer processes

Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry and Green Chemistry Center, Peking University, 202 Chengfu Road, 098#, Beijing 100871, China State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 200060, China

Transition-Metal-Free Coupling Reactions

Publisher Summary This chapter focuses on the electron transfer reactions in organic chemistry. The simplest elementary act in homogeneous solution chemistry is the exchange of an electron between two chemical entities. No bonds need to be formed or broken in the process, and if the two species are identical, except for a difference in oxidation state, no net chemical change takes place. Such self-exchange reactions constitute the basis of theoretical treatments of electron transfer. A more complex and chemically interesting situation is the electron-transfer reaction between two species of different chemical composition. In electron-transfer theory, it is an important postulate that electrons are transferred one by one, which does not mix well with the two-electron centered electronic theory of organic molecules. Organic electron transfers rarely occur as isolated steps because of the high chemical reactivity of odd-electron species. Processes involving one or several electron-transfer steps are not likely to preserve the stereochemical integrity of the reactants. With the present upsurge of research studies frequently invoking organic electron-transfer steps in mechanistic discussions, there is a great need of a theoretical background applicable to organic species and compatible with the language of physical organic chemistry.

Electron transfer reactions in organic chemistry

Utilisation de 3 methodes electrochimiques pour determiner les reactivites d'une serie de 26 couples radical aryl-nucleophile

Nucleophile and aryl radical reactivity in SRN1 aromatic nucleophilic substitution reactions. Absolute and relative electrochemical determination

Electrochemical inducement of aromatic nucleophilic substitution of ArX compounds is investigated for a number of substrate and nucleophile systems in liquid ammonia. Electron transfer to the Armradical resulting from the initial reductive cleavage is essentially the only reaction competing with substitution. The competition occurs under two different regimes in- volving either homogeneous or heterogeneous electron transfer leading to different kinds of kinetic control. Cyclic voltammetry is used both for a rapid estimate of the nucleophile reactivity and for a quantitative determination of the rate constants of the nucleophile addition on Are. The method is also applied to the determination of the kinetic stabilities of the substrate anion rad- icals which is not possible through the standard application of electrochemical techniques. The agreement of the predicted ki- netics with the experimental data both under homogeneous and heterogeneous electron transfer conditions provides further support for the SRNI mechanism.

Electrochemically induced aromatic nucleophilic substitution in liquid ammonia. Competition with electron transfer

Electrochemically catalyzed aromatic nucleophilic substitution. Phenoxide ion as nucleophile

Aryl radicals from electrochemical reduction of aryl halides. Addition on olefins

Electron transfer induced reactions. Electrochemically stimulated aromatic nucleophilic substitution in organic solvents

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