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Compounds comprising S–S bonds serve as significant pharmacological scaffolds in medicinal chemistry and natural products. We have devised an efficient electrochemical method for the construction of asymmetric disulfide bonds, leading to the synthesis of unsymmetric thiosulfonates. Compared with existing synthesis methods, our work not only avoids the use of metals and oxidants, but also realizes the operation of a one-pot three-component method, which makes this strategy extremely attractive. [ABSTRACT FROM AUTHOR]

2‐(chalcogen)benzothiazoles are frequently used as core structures for the development of pharmaceutical agents. A strategy for the synthesis of 2‐(chalcogen)benzothiazoles under electrooxidative conditions using isocyanides, thiols or diselenides as substrates was developed. This protocol allows access to structurally diverse 2‐(chalcogen)benzothiazoles in good yields and with good functional group tolerance, which does not require heavy metal catalysts and exogenous oxidants. Furthermore, gram‐scale synthesis was performed to demonstrate the scale‐up applicability of this reaction. [ABSTRACT FROM AUTHOR]

A mild and efficient electrochemical method for radical addition, cyclization, and migration reaction was described in this work. A difluoromethyl radical was produced by anodizing CF2HSO2Na. The resulting product was then added to olefin, underwent Smiles cyclization, and migrated to form β-difluoromethamide compounds after the release of SO2. The process was free from metals and catalysts, gram-grade, and resistant to a variety of electron-rich substrates. [ABSTRACT FROM AUTHOR]

Homogeneous electrocatalysts can indirect oxidate the high overpotential substrates through single‐electron transfer on the electrode surface, enabling efficient operation of organic electrosynthesis catalytic cycles. However, the problems of this chemistry still exist such as high dosage, difficult recovery, and low catalytic efficiency. Single‐atom catalysts (SACs) exhibit high atom utilization and excellent catalytic activity, hold great promise in addressing the limitations of homogeneous catalysts. In view of this, we have employed Fe‐SA@NC as an advanced redox mediator to try to change this situation. Fe‐SA@NC was synthesized using an encapsulation‐pyrolysis method, and it demonstrated remarkable performance as a redox mediator in a range of reported organic electrosynthesis reactions, and enabling the construction of various C−C/C−X bonds. Moreover, Fe‐SA@NC demonstrated a great potential in exploring new synthetic method for organic electrosynthesis. We employed it to develop a new electro‐oxidative ring‐opening transformation of cyclopropyl amides. In this new reaction system, Fe‐SA@NC showed good tolerance to drug molecules with complex structures, as well as enabling flow electrochemical syntheses and gram‐scale transformations. This work highlights the great potential of SACs in organic electrosynthesis, thereby opening a new avenue in synthetic chemistry. [ABSTRACT FROM AUTHOR]

This article explores the use of N-heterocyclic carbenes (NHCs) in photochemical and electrochemical catalysis for organic synthesis. NHCs have unique catalytic properties and are cost-effective and environmentally friendly. The article discusses various reactions mediated by NHCs, including the formation of C-O and C-N bonds. It also highlights the combination of NHC catalysis with photoredox catalysis for radical reactions, such as alkylation and benzylation of alkenes. The article emphasizes the potential of NHC and photoredox catalysis in enabling the construction of diverse organic compounds under mild conditions. Additionally, it presents examples of NHC-mediated reactions and discusses future research opportunities in this field. [Extracted from the article]

Alkenylboronates are highly versatile building blocks and valuable reagents in the synthesis of complex molecules. Compared with that of monosubstituted alkenylboronates, the synthesis of multisubstituted alkenylboronates is challenging. The copper‐catalyzed carboboration of alkynes is an operationally simple and straightforward method for synthesizing bis/trisubstituted alkenylboronates. In this work, a series of copper‐metallized N‐Heterocyclic Carbene (NHC) ligand porous polymer catalysts are designed and synthesized in accordance with the mechanism of carboboration. By using CuCl@POL‐NHC‐Ph as the optimal nanocatalyst, this study realizes the β‐regio‐ and stereoselective (syn‐addition) 1,2‐carboboration of alkynes (regioselectivity up to >99:1) with satisfactory yields and a wide range of substrates. This work not only overcomes the selectivity of carboboration but also provides a new strategy for the design of nanocatalysts and their application in organic synthesis. [ABSTRACT FROM AUTHOR]

The oxygen evolution reaction (OER), characterized by a four‐electron transfer kinetic process, represents a significant bottleneck in improving the efficiency of hydrogen production from water electrolysis. Consequently, extensive research efforts have been directed towards identifying single‐atom electrocatalysts with exceptional OER performance. Despite the comprehensive understanding of the OER mechanism, its application to other valuable synthetic reactions has been limited. Herein, we leverage the MOOH intermediate, a key species in the Mn−N−C single‐atom catalyst (Mn‐SA@NC), which can be cyclically delivered in the OER. We exploit this intermediate' s capability to facilitate electrophilic transfer with silane, enabling efficient silane oxidation under electrochemical conditions. The SAC electrocatalytic system exhibits remarkable performance with catalyst loadings as low as 600 ppm and an exceptional turnover number of 9132. Furthermore, the catalytic method demonstrates stability under a 10 mmol flow chemistry setup. By serving as an OER electrocatalyst, the Mn‐SA@NC drives the entire reaction, establishing a practical Mn SAC‐catalyzed organic electrosynthesis system. This synthesis approach not only presents a promising avenue for the utilization of electrocatalytic OER but also highlights the potential of SACs as an attractive platform for organic electrosynthesis investigations. [ABSTRACT FROM AUTHOR]

Methanol is an important C1 source in organic synthesis because of its low cost, abundance, and biodegradability. Therefore, using methanol as a C1 source to synthesize high-value-added compounds is crucial. This review highlights the recent advances in various electrochemical and photochemical reactions using methanol as a sustainable source. This study mainly introduces the reaction of methylation, methoxylation, hydroxymethylation, and cyclization under the conditions of light and electricity. The reaction mechanisms of these reactions are also discussed. This study provides a reference for the future application of this kind of reaction in organic synthesis. [ABSTRACT FROM AUTHOR]

N‐(α‐alkoxyalkyl)benzotriazoles are of great importance for biochemical and antitumor activity. A feasible protocol has been developed for the synthesis of N‐(α‐alkoxyalkyl)benzotriazoles using azoles, aldehydes and alcohols as substrates under electrochemical conditions. The reaction is carried out under acid catalyst‐ and oxidant‐free conditions, so that a variety of synthetically useful nitrogen heterocyclic derivatives can be obtained. More meaningfully, a gram‐scale synthetic approach was employed to demonstrate the scale‐up applicability of this transformation. [ABSTRACT FROM AUTHOR]

Synthesis of organotellurium compounds is crucial in pharmaceutical sciences. Herein, a novel and efficient electrochemically catalyzed multicomponent reaction of propargylamide or propargylamine with CO2 and ditellurium has been developed, and a variety of tellurium-containing 2-oxazolidinones were synthesized for the first time to the best of our knowledge with satisfactory yields under mild conditions. In addition, the resulting tellurium-containing 2-oxazolidinones were tested for in vitro anticancer activity by using the MTT assay against various types of human cancer cells. Compound 5e showed better antitumor activity than did the other oxazolidinone and selenium-containing oxazolidinone compounds. These findings have provided new synthetic strategies for organotellurium compounds and have shown a new perspective for the study of the biological activity of chalcogen-containing organic compounds. [ABSTRACT FROM AUTHOR]

Carbon dioxide is a harmful greenhouse gas, as well as a valuable resource. Here, a three‐component cyclization reaction was developed for the synthesis of oxazolidine‐2,4‐diones by immobilizing CO2 under the electrochemistry and copper catalyst. Propargyl amide was used as the reaction substrate to capture carbon dioxide to produce carboxyl anion, while selenide produced electrophilic receptor to activate the triple bond under electrochemical conditions. Then, intramolecular cyclization reaction was carried out to obtain the target product. Through this environmentally friendly strategy, a series of important oxazolidine‐2,4‐diones was synthesized. [ABSTRACT FROM AUTHOR]

Industrial waste gas is one of the major sources of atmospheric CO2, yet the direct conversion of the low concentrations of CO2 in waste gases into high value‐added chemicals have been a great challenge. Herein, a copper‐based N‐heterocyclic carbene porous polymer catalyst (Cu@NHC‐1) for the direct conversion of low concentration CO2 into oxazolidinones was successfully fabricated via a facile copolymerization process followed by the complexation with Cu(OAc)2. A continuous flow device was designed to deliver a continuous and stable carbon source for the reaction. Due to the triple synergistic effect of its porous structure, nitrogen activation sites and catalytic Cu center, Cu@NHC‐1 shows highly efficient and selective adsorption, activation, and conversion of the low concentration CO2 (30 vol%). Its practical application potential is demonstrated by the ability to successfully convert the CO2 in lime kiln waste gas into oxazolidinones in satisfactory yields under mild conditions. [ABSTRACT FROM AUTHOR]

During the chlor-alkali process, in operation since the nineteenth century, electrolysis of sodium chloride solutions generates chlorine and sodium hydroxide that are both important for chemical manufacturing1–4. As the process is very energy intensive, with 4% of globally produced electricity (about 150 TWh) going to the chlor-alkali industry5–8, even modest efficiency improvements can deliver substantial cost and energy savings. A particular focus in this regard is the demanding chlorine evolution reaction, for which the state-of-the-art electrocatalyst is still the dimensionally stable anode developed decades ago9–11. New catalysts for the chlorine evolution reaction have been reported12,13, but they still mainly consist of noble metal14–18. Here we show that an organocatalyst with an amide functional group enables the chlorine evolution reaction; and that in the presence of CO2, it achieves a current density of 10 kA m−2 and a selectivity of 99.6% at an overpotential of only 89 mV and thus rivals the dimensionally stable anode. We find that reversible binding of CO2 to the amide nitrogen facilitates formation of a radical species that plays a critical role in Cl2 generation, and that might also prove useful in the context of Cl− batteries and organic synthesis19–21. Although organocatalysts are typically not considered promising for demanding electrochemical applications, this work demonstrates their broader potential and the opportunities they offer for developing industrially relevant new processes and exploring new electrochemical mechanisms.A study shows that an organocatalyst with an amide functional group, and carbon dioxide, can efficiently and selectively produce chlorine, potentially offering a low-cost and less energy intensive alternative to the chlor-alkali process. [ABSTRACT FROM AUTHOR]