Self-Standing Metal Foam Catalysts for Cathodic Electro-Organic Synthesis.

Although electro-organic synthesis is currently receiving renewed interest because of its potential to enable sustainability in chemical processes to value-added products, challenges in process development persist: For reductive transformations performed in protic media, an inherent issue is the limited choice of metallic cathode materials that can effectively suppress the parasitic hydrogen evolution reaction (HER) while maintaining a high activity toward the targeted electro-organic reaction. Current development trends are aimed at avoiding the previously used HER-suppressing elements (Cd, Hg, and Pb) because of their toxicity. Here, this work reports the rational design of highly porous foam-type binary and ternary electrocatalysts with reduced Pb content. Optimized cathodes are tested in electro-organic reductions using an oxime to nitrile transformation as a model reaction relevant for the synthesis of fine chemicals. Their electrocatalytic performance is compared with that of the model CuSn7Pb15 bronze alloy that has recently been endorsed as the best cathode replacement for bare Pb electrodes. All developed metal foam catalysts outperform both bare Pb and the CuSn7Pb15 benchmark in terms of chemical yield and energetic efficiency. Moreover, post-electrolysis analysis of the crude electrolyte mixture and the cathode's surfaces through inductively coupled plasma mass spectrometry (ICP-MS) and scanning electron microscopy (SEM), respectively, reveal the foam catalysts' elevated resistance to cathodic corrosion.

Paraformaldehyde as C1 Synthon: Electrochemical Three-Component Synthesis of Tetrahydroimidazo[1,5-a]quinoxalin-4(5H)-ones in Aqueous Ethanol.

A green and practical method for the electrochemical synthesis of tetrahydroimidazo[1,5-a]quinoxalin-4(5H)-ones through the three-component reaction of quinoxalin-2(1H)-ones, N-arylglycines and paraformaldehyde was reported. In this strategy, EtOH played dual roles (eco-friendly solvent and waste-free pre-catalyst) and the in situ generated ethoxide promoted triple sequential deprotonations.

Electrochemical Synthesis and Reactivity of Three-Membered Strained Carbo- and Heterocycles.

Three-membered carbocyclic and heterocyclic ring structures are versatile synthetic building blocks in organic synthesis with biological importance. Moreover, the inherent strain of these three-membered rings leads to their ring-opening functionalization through C->C, C->N, and C-O bond cleavage. Traditional synthesis and ring-opening methods for these molecules require the use of acid catalysts or transition metals. Recently, electro-organic synthesis has emerged as a powerful tool for initiating new chemical transformations. In this review, the synthetic and mechanistic aspects of electro-mediated synthesis and ring-opening functionalization of three-membered carbo- and heterocycles are highlighted.

Electrochemical Iodination through the In Situ Generation of Iodinating Agents: A Promising Green Approach.

The synthesis of iodinated compounds using cheap, simple, and green strategies is of fundamental importance. Iodination reactions are mainly used to synthesize useful intermediates, especially in the pharmaceutical field, where they are employed for the production of contrast media or of iodinated active pharmaceutical ingredients. Traditional synthetic methods suffer from the use of erosive, toxic, or hazardous reactants. Approaches which involve the use of molecular iodine as an iodinating agent require the addition of an oxidizing agent, which is often difficult to handle. Electrochemistry can offer a valid and green alternative by avoiding the addition of such oxidizing agents, transforming the iodine source in the active species through the use of electrons as the main reactants. Herein, we report the electrochemical iodination with the generation of iodinating species in situ in water by using iodides as the source of iodine atoms. First of all, the electrochemical behavior of iodide and iodine in water on carbonaceous anodes was studied and, after selecting the suitable potential, in situ electrochemical iodination was successfully applied to 5-hydroxyisophthalic acid and 5-sulfosalicylic acid, comparing the iodinating power of I2 and iodonium species.

Direct Electrochemical Synthesis of 2,3-Disubstituted Quinoline N-oxides by Cathodic Reduction of Nitro Arenes.

The use of electric current in synthetic organic chemistry offers a sustainable tool for the selective reductive synthesis of quinoline N-oxides starting from easily accessible nitro compounds. The reported method employs mild and reagent-free conditions, a simple undivided cell, and constant current electrolysis set-up which provides conversion with a high atom economy. The synthesis of 30 differently substituted quinoline N-oxides was successfully performed in up to 90 % yield. Using CV studies, the mechanism of the selective formation of the quinoline N-oxides was elucidated. The technical relevance of the described reaction could be shown in a 50-fold scale-up reaction.

Aqueous OH-/H+ dual-ion gradient assisted electricity effective electro-organic synthesis of 2,5-furandicarboxylic acid paired with hydrogen fuel generation.

The OH-/H+ dual-ion gradient has a hidden electromotive force of 0.82 V under standard conditions; however, its non-redox nature completely prevents its direct interconversion as electrical driving force. We show by using organic molecules whose heterogeneous electron transfer is pH dependent, OH-/H+ dual-ion energy can be directly harvested as electrical driving force for performing simultaneous electro-organic synthesis and hydrogen fuel production in an electricity effective manner. To demonstrate this dual-ion gradient assisted electro-organic synthesis, 5-hydroxymethylfurfural (HMF) is chosen as the model molecule because of the immense techno commercial applications of its oxidized products. This dual-ion assisted device only required âˆ¼1 V to provide a current density of 50 mA/cm2 and for achieving the same rate; the traditional state-of-the-art electrolytic cell required a doubling of the applied potential. The dual-ion gradient assisted device can convert biomass-derived HMF to economically important FDCA with âˆ¼90 % yield and âˆ¼87 % Faradaic efficiency with simultaneous H2 fuel production at a potential as low as 1 V.

Electro-Synthesis of Organic Compounds with Heterogeneous Catalysis.

Electro-organic synthesis has attracted a lot of attention in pharmaceutical science, medicinal chemistry, and future industrial applications in energy storage and conversion. To date, there has not been a detailed review on electro-organic synthesis with the strategy of heterogeneous catalysis. In this review, the most recent advances in synthesizing value-added chemicals by heterogeneous catalysis are summarized. An overview of electrocatalytic oxidation and reduction processes as well as paired electrocatalysis is provided, and the anodic oxidation of alcohols (monohydric and polyhydric), aldehydes, and amines are discussed. This review also provides in-depth insight into the cathodic reduction of carboxylates, carbon dioxide, CC, C≡C, and reductive coupling reactions. Moreover, the electrocatalytic paired electro-synthesis methods, including parallel paired, sequential divergent paired, and convergent paired electrolysis, are summarized. Additionally, the strategies developed to achieve high electrosynthesis efficiency and the associated challenges are also addressed. It is believed that electro-organic synthesis is a promising direction of organic electrochemistry, offering numerous opportunities to develop new organic reaction methods.

Electro-organic synthesis of tetrahydroimidazo[1,2-a]pyridin-5(1H)-one via a multicomponent reaction.

Electro-synthesis through a one-pot three-component condensation of corresponding aldehydes, Meldrum's acid, and 2-(nitromethylene)imidazolidine resulted in a series of novel tetrahydroimidazo[1,2-a]pyridine-5(1H)-one derivatives containing an electronegative pharmacophore (=CNO2). The process was carried out in propanol medium with sodium bromide presented as electrolyte, inside an undivided cell with good to excellent yields. As a powerful entry into fused polycyclic structures related to bioactive heterocycles, this green protocol shows great potential.

Advances in Electrochemical Decarboxylative Transformation Reactions.

Owing to their non-toxic, stable, inexpensive properties, carboxylic acids are considered as environmentally benign alternatives as coupling partners in various organic transformations. Electrochemical mediated decarboxylation of carboxylic acid has emerged as a new and efficient methodology for the construction of carbon-carbon or carbon-heteroatom bonds. Compared with transition-metal catalysis and photoredox catalysis, electro-organic decarboxylative transformations are considered as a green and sustainable protocol due to the absence of chemical oxidants and strong bases. Further, it exhibits good tolerance with various functional groups. In this Minireview, we summarize the recent advances and discoveries on the electrochemical decarboxylative transformations on C-C and C-heteroatoms bond formations.