Herein, the first use of CHCl3 as a "traceless" reagent to trigger a 1,2-aryl migration for the synthesis of vinyl ketones has been developed. Its success relies on a continuous-flow strategy that harnesses the synergistic cathodic reduction of CHCl3 and anodic oxidation of Cl- and carbon-centered radicals. This electrochemical method operates under catalyst-free conditions and employs low-concentration electrolytes along with low-cost electrodes, thereby enhancing its practicality and sustainability.

State-of-the-art macrolactone synthesis predominantly relies on the end-to-end cyclization of seco-acids, a strategy that requires high-dilution conditions (<5 mM) to suppress oligomerization. To address this limitation, we report an electrochemical macrolactonization protocol that operates at a significantly higher concentration (50 mM). Leveraging an iodide/PPh3 dual-mediation system, this method provides access to 5- to 21-membered lactones and accommodates O-, S-, and N-heteroatom functionalization. Its efficacy originates from the gradual, charge-consumption-dependent formation of an acyloxyphosphonium intermediate, which maintains a relatively low local concentration despite high substrate loading.

Electrochemical preparation and transformation of sulfonium ions have been paid increasing attention. Herein, we have developed an efficient electrochemical approach for the α‐C(sp3)‐H functionalization of aryl ketones via sulfonium salt pool. The reaction proceeds under constant current conditions at ambient temperature, avoiding the complex low‐temperature operation typically required in the electrochemical generation of cation pools, and allowing the use of oxidatively sensitive nucleophiles, particularly ones with less positive potential than that of thianthrene as reaction partners, for downstream functionalization.

The radical allylic substitution of free allylic alcohols remains a challenge. Herein, we report an electrochemical strategy that facilitates the dehydroxylative allylic trifluoromethylation of unprotected allylic alcohols with thianthrenium salts, affording trisubstituted alkenes with high regio- and E/Z selectivities. The key to this success lies in the electrochemical unlocking of the unique trifunctionality of thianthrenium salts, which serve synergistically as radical precursors, sacrificial anodic agents, and deoxygenation mediators.

We developed a double-consecutive paired electrolysis system that enables the Minisci-type alkylation of quinoxalinone with alcohols under mild conditions. Using PPh3 as the deoxygenation reagent and iodide as the redox mediator, the direct activation and cleavage of the alcoholic C-O bond were achieved without any preactivation step. Since the electrolysis occurs at the oxidation potential of iodide, which is much lower than that of alcohols, alkyl radicals are thus generated under mild conditions.

Herein, the first use of CHCl 3 as a “traceless” reagent to trigger a 1,2‐aryl migration for the synthesis of vinyl ketones has been developed. Its success relies on a continuous‐flow strategy that harnesses the synergistic cathodic reduction of CHCl 3 and anodic oxidation of Cl − and carbon‐centered radicals. This electrochemical method operates under catalyst‐free conditions and employs low‐concentration electrolytes along with low‐cost electrodes, thereby enhancing its practicality and sustainability.

Ketyl radicals are pivotal intermediates for constructing secondary and tertiary alcohols. This review summarizes recent advances (since 2024) in their electrochemical generation via umpolung of carbonyl compounds. Unlike traditional methods, these approaches avoid strong reductants or photocatalysts, offering improved sustainability, enhanced selectivity, and broad functional‐group tolerance under mild conditions. The content is organized by reaction type—including radical cross‐coupling, additions to unsaturated systems, and related transformations. This review emphasizes mechanistic insights and substrate scope, and concludes with an outlook on future directions to inform ongoing research in the field.

The catalytic upgrading of bulk feedstock chemicals into value-added products represents a powerful approach in modern chemical synthesis. Herein, we describe an iron-catalyzed photoelectrochemical strategy that enables the efficient conversion of nitromethane (MeNO2), an abundant industrial feedstock, into synthetically valuable nitric oxide (·NO). This proof-of-concept platform allows the direct synthesis of structurally diverse oximes from MeNO2 and alcohols and exhibits broad functional group tolerance, including compatibility with carbonyl groups and acid-sensitive motifs such as esters and silyl ethers. Mechanistic investigations reveal that the iron catalyst plays a dual role: promoting radical deformylation of alcohols or ring-opening of cycloalkanols and mediating the conversion of MeNO2 into ·NO.

Organic electrosynthesis has recently emerged as an indispensable tool in the green synthesis toolbox. In electrochemical synthesis, two key issues require special attention: first, it is desirable to lower the redox potentials of substrates to ensure good selectivity and functional group compatibility. Second, regarding constant current electrolysis, it is crucial to increase the redox potential gap between substrates and their corresponding products to prevent over-oxidation or over-reduction, thereby enhancing reaction selectivity. Non-covalent interactions (e.g., hydrogen bond, halogen bond, and ion pairing) provide an effective strategy to achieve these goals. In this Feature Article, we review representative examples demonstrating the application of non-covalent interactions in organic electrosynthesis. Finally, we discuss the remaining challenges and future prospects in this field.

Despite its potential, the radical-mediated 1,2-arylheteroarylation of alkenes for constructing valuable 1,2-arylheteroaryl ethane motifs remains underdeveloped. We herein report an alternative continuous-flow electrochemical approach using alkenes, aryl bromides, and cyanopyridines as coupling partners. This method eliminates the need for sacrificial anodes, catalysts, or chemical oxidants, requires minimal electrolyte, and achieves high regioselectivity. Its utility is underscored by successful applications in the late-stage functionalization of bioactive molecules.

In contrast to radical‐mediated electrochemical decarboxylative couplings, electrochemical decarboxylative functionalizations proceeding through carbocation intermediates (Hofer‐Moest pathway) unlock unique reactivity and selectivity. These in situ‐generated carbocations can be trapped by diverse nucleophiles or undergo elimination to form alkenes, significantly expanding synthetic versatility. This review systematically surveys advances in electrochemical Hofer‐Moest‐type reactions since 2019, categorizing transformations by bond‐forming events (CN, CO, CP, CF, CC, and CC). Beyond summarizing key breakthroughs, it also provide balanced evaluation of current limitations to delineate the scope and applicability of these methods. Finally, persistent challenges are outlined and future research directions in this emerging field is proposed.

The deuterated thiol–yne reaction using D 2 O represents an attractive strategy for simultaneously introducing pharmaceutically relevant C(sp 2 )─D bonds and vinyl sulfide motifs. However, achieving high deuterium (D) incorporation remains a significant challenge. Herein, we report an electrochemical deuterated thiol–yne reaction that delivers D‐containing vinyl sulfides with up to 98% alkene selectivity and 99% D incorporation, employing disulfides (RSSR) and D₂O over an in situ sulfur‐modified nickel foam (NF) electrode. Mechanistic studies reveal a reductive cleavage of RSSR to RS⁻ intermediates, which subsequently form surface nickel sulfide (NiS x ) species through R─S bond cleavage. In situ and ex situ characterizations confirm the NiS x formation and its role in reducing alkene adsorption, thereby suppressing its overreduction. This strategy demonstrates broad applicability across terminal and internal alkynes, as well as aromatic and aliphatic disulfides, furnishing 30 diverse examples of D‐labeled vinyl sulfides.

We report an electrochemical radical‐polar crossover (RPC) strategy for the radical cyclization of olefinic amides with C−H nucleophiles with H2 as the byproduct. Enabled by this strategy, structurally diverse multi‐ester functionalized benzoxazines and iminoisobenzofurans were obtained with good yields. Notably, the resulting triple‐ester functionalized O‐heterocycles are inaccessible by other means. This protocol features catalyst‐ and external oxidant‐free conditions, high atom economy, and broad substrate scope. The scalable synthesis as well as product derivatization highlight the synthetic utility of this electrochemical protocol.

The electrochemical catalyst‐free generation of carbon radicals bearing three electron‐withdrawing groups from the corresponding C−H nucleophiles remains unexplored. To this end, we report a direct electro‐oxidation strategy to access these electrophilic carbon radicals under catalyst‐free conditions. Enabled by this strategy, the radical 1,2‐alkylarylations of allylic alcohols was realized, affording β‐quaternary ketones with high functional group compatibility. This protocol is operationally simple and also easy to scale up.

A visible-light-enabled, photocatalyst-free hydroacylation reaction of azodicarboxylic acid derivatives was described. This radical conjugate addition (RCA) protocol relied on the dual role of 4-acyl-1,4-dihydropyridine (acyl-DHP) reagents that besides being as radical reservoirs, they also enabled the conversion of radical adducts to anion intermediates via reduction. Under "catalyst-oxidant-additive free" conditions, a wide range of structurally different acyl hydrazide products were readily obtained in 56%-99% yields. The utility of this transformation was further demonstrated by the scale-up synthesis and downstream derivatization.

The merger of organic electrosynthesis with 3d transition-metal catalysis has offered huge opportunities for modern organic synthesis. This review summarizes the key advancements in this direction published in the recent two years.

We report an electrophotoredox cerium-catalyzed LMCT strategy to incorporate carboxylic acids into radical cyclization cascades. This protocol provides a solution to address the challenges in alkylated benzimidazo-fused isoquinolinone synthesis.

Ketyl radicals display new reactivities beyond the intrinsic electrophilicity of carbonyls. Recently, the bloom of organic electrosynthesis has fueled the evolution of the generation and harnessing of ketyl radcials under “greener” conditions. This graphical review summarizes these electrochemical advancements into three major categories: cross-pinacol couplings, coupling of carbonyls with alkyl radical precursors, and coupling of carbonyls with unsaturated systems (alkenes, alkynes, cyanoarenes, and N-heterocycles).

The electro-generation of acyl radicals from both aromatic and aliphatic aldehydes is a synthetic challenge. We addressed this challenge by merging electro-oxidation and a quinuclidine-mediated HAT strategy.

A formal [3+3] annulation of 3-aminopyrazoles with cinnamaldehydes or cinnamyl alcohols mediated by NH4SCN has been developed. This protocol provides a practical route to construct 5-arylated pyrazolo[1,5-a]pyrimidines with high functional group tolerance. The use of NH4SCN as the cyanide anion surrogate allows the transient generation of cyanohydrin, which shifts the reactive center within cinnamaldehydes from formyl group to alkene group to realize an opposite regiocontrol comparing with previous reports.